Colour changing composition in gel form

ABSTRACT

A changing color composition in the form of a gel for caring for and/or making up keratin materials is disclosed. The composition comprises in a physiologically acceptable medium, a) from 0.1 to 10% by weight preferably from 0.5 to 10% more preferably from 1 to 5% by weight relative to the weight of the composition of microcapsules containing releasable colorant(s), said microcapsules comprising: —a core comprising one organic material, —at least one layered coating surrounding said core, the layered coating comprising at least one polymer at least one colorant, and advantageously at least one lipid-based material, b) at least 3% by weight, preferably at least 5% by weight, more preferably at least 8% by weight and advantageously at least 10% by weight relative to the weight of the composition of an aqueous phase comprising water and at least one compound chosen from polyols, glycols and C2-C8 monoalcohols, and mixtures thereof, and c) at least one hydrophilic gelifying agent.

TECHNICAL FIELD

The present invention relates to a color-changing composition in theform of a transparent gel in particular useful for care, hygiene and/ormakeup of keratin materials.

In particular, a color-changing composition according to the inventionmay be any type of cosmetic composition such as a foundation, a facepowder, an eye shadow, a concealer product, a blusher, a lipstick, a lipbalm, a lip gloss, a lip pencil, an eye pencil, an eyeliner, a mascara,a body makeup product, a skin colouring product, a care product such asa care cream, a ‘BB’ product (Blemish Balm product able to coverimperfections), a tinted cream or an antisun product, preferably afoundation or BB product.

A composition of the invention is especially a composition intended tobe applied to a keratin material, in particular the skin and moreparticularly facial skin, such as a skin care or make-up product forface.

According to another embodiment, the composition of the invention is amascara.

According to another embodiment, the composition of the invention is aproduct for lips, in particular a lipgloss, a lipbalm or a lipstick.

BACKGROUND

Cosmetic compositions, especially foundations, are commonly used to givethe skin an aesthetic colour, but also to hide skin imperfections suchas redness and/or marks. In this regard, many formulations have beendeveloped to date.

In this respect, there is a growing interest in cosmetic products thatprovide a change in color in response to external incentives such forexample shear force.

Generally, this purpose is achieved by including in cosmetic compositionmicroencapsulated colorants wherein, upon application on the skin, thecomposition provides the expected changing color. More particularly, thechange of color is provided by the colorant-containing microcapsules,which upon rupture by application of a mechanical force, release theentrapped colorant into the composition, thereby changing its color. Amechanical action such as rubbing spread the topical composition andfacilitates its penetration into the skin. The immediate change of colorof the composition provides a visual esthetical effect.

Different types of entrapped colorants and more particularlypigments-containing microcapsules are already available. They mainlydiffer through the type of entrapping material(s) and/or the type ofencapsulation.

Thus, as pigments encapsulated by microcapsules in acrylic acid and/ormethacrylic acid polymers or copolymers, it may be cited for examplemicrocapsules containing copolymer of ethyl acrylate/methacrylic acidammonium salts, commercialized by the Tagra company and described inWO-A-01/35933. It may be also cited the encapsulated pigmentscommercialized by TAGRA BIOTECHNOLOGIES under the name BLACKCAP1©,YELLOWCAP1©, REDCAP1©, BLACKCAP3©, YELLOWCAP3©, REDCAP3©.

As pigments encapsulated by microspheres in cellulose derivatives, itcan be cited for example spheres comprising cellulose, hydroxypropylmethylcellulose, commercialized by the Induchem company under the nameUnisphere©.

As pigments encapsulated by microcapsules in polymers of polyester,polyaminomethacrylate, polyvinylpyrrolidone,hydroxypropylmethylcellulose, shellac types and mixtures thereof, it maybe notably cited those described in the application US 2011/0165208 ofBiogenics and commercialized under the name Magicolor© by Biogenics.

As other pigments encapsulated by microcapsules may also be cited theones disclosed by DAITO in JP2011-79804, these pigment-encapsulateddouble-layer microcapsules comprising three or more of the following (a)mannitol, (b) hydrogenated lecithin, (c) polymethylmethacrylate, (d)cellulose and (e) shellac.

These double-layer microcapsules do not comprise an uncoloured core asthe one of the microcapsules preferably used according to the invention,but rather a colored inner layer containing the aforesaid componentswhich are mixed all together and then granulated.

However, with some colorant-containing microcapsules it may be difficultto permanently retain the colorant over long periods of time and whensubjected to different environments and conditions. This is true ofpigments, oil soluble dyes, and water soluble dyes. Thus, somemicrocapsules described in patents and publications have been found togradually release the colorant, or to “bleed”, over time when tested forprolonged periods at elevated temperatures. Color bleed occurs when adye or pigment migrates through or off of microspheres/microcapsulesthrough contact with moisture and/or other ingredients in a formulationsuch as alcohols or glycols, surfactants, silicones, oils,preservatives, salts and other components typically found in cosmeticformulations. Leeching or bleed of the colorant in cosmetic compositioncan impair the long term visual effect of the cosmetic both in thecontainer and on the substrate.

Furthermore, some pigment-containing microcapsules may confer a lowercovering effect than expected.

Furthermore, some pigment-containing microcapsules are immediatelybroken down at the time of application so, while there is the fun of asudden colour change, it has not been possible to realise intermediatestages in this colour change or to adjust the colour gradation.

Furthermore, some pigment-containing microcapsules may have somestability issues depending on the cosmetic composition and associatedsolvents/ingredients.

Furthermore, some pigment-containing microcapsules may have a grey coloraspect that confers a not attractive color in the bulk of the cosmeticcomposition.

At last, some microcapsules may provide a discomfort and/or unfavourablefeeling when the cosmetic formulation including them is applied on akeratin material.

As far as transparent gels are concerned, the technical problem was topropose a composition with cleaning, caring and transparent appearancewhich provides good makeup effects, particularly a good covering effect.Transparent gel usually attracts lots of consumers by its watery,breathable, cute, beautiful and transparent bulk appearance, whichdelivers a message of fresh, watery, hydrating and caring perception toconsumer. However, there is a need of a product, which can be pure andclean as transparent gel, but can still deliver some makeup results.

Technical barriers for design this kind of products, are first thedifficulty to wrap pigment in transparent gel and still keep itstransparency, secondly the bad compatibility of microcapsules for waterytransparent gel, thirdly the hardness of the microcapsules: they are noteasy to be broken and as as consequence the sensory of gel afterapplication will be dry.

SUMMARY

Thus there is a need to provide cosmetic gel with colorant-containingmicrocapsules having improved color bleed resistance. In this respect,there is a need of colorant-containing microcapsules, which capsulesretain good shatter resistance and exhibit improved bleed resistance. Ina cosmetic composition if the dye is not permanently retained, this canimpair the long-term visual effect of the cosmetic.

There is also a need to provide a cosmetic gel which allows thepreferred colouration or gradation pattern to be adjusted by varying themethod or intensity of application onto the skin or the use ofmicrocapsules containing different colorants.

There is also a need to provide a cosmetic gel stable with a large panelof solvent/ingredient associated.

There is also a need to provide a cosmetic gel wherein the microcapsulesare or are not visible inside the bulk of the composition depending onthe desired appearance.

There is also a need for a cosmetic gel containing pigment-encapsulatedmicrocapsules which do not provoke to the user a discomfort feeling whenapplied.

There is also a need to provide a cosmetic composition containingpigment-encapsulated microcapsules which disintegrate rapidly indeedimmediately when applied, with a liquid feeling on the skin and leadingto coloured compositions devoid of any granular aspect. Particularly,the composition may present different shades or color gradationsdepending on the rubbing strength.

There is also a need to provide pigment-encapsulated microcapsules witha hardness sufficient to be compounded in an industrial process withoutalteration. Advantageously the hardness of the microcapsules does notsignificantly decrease during the preparation process.

There is also a need to have at disposal cosmetic composition to obtainan aqueous gel with an homogeneous dispersion of particles.

Surprisingly and advantageously, the compositions according to theinvention meet the needs of the prior art.

Thus, according to one of its aspects, a subject of the invention is achanging colour composition on the form of a gel for caring for and/ormaking up keratin materials comprising, in a physiologically acceptablemedium,

a) from 0.1 to 10% by weight preferably from 0.5 to 10% more preferablyfrom 1 to 5% by weight relative to the weight of the composition ofmicrocapsules containing releasable colorant(s), said microcapsulescomprising:

-   -   a core comprising one organic material,    -   at least one layered coating surrounding said core, the layered        coating comprising        -   at least one polymer,        -   at least one colorant,        -   and advantageously at least one lipid-based material,

b) at least 3% by weight, preferably at least 5% by weight, morepreferably at least 8% by weight and advantageously at least 10% byweight relative to the weight of the composition of an aqueous phasecomprising water and at least one compound chosen from polyols, glycols,C₂-C₈ monoalcohols, and mixtures thereof,

c) at least one hydrophilic gelifying agent.

Advantageously, the microcapsules comprise at least two layers,preferably at least one organic inner layer and one organic outer layerof different colour.

Preferably the core comprises at least one monosaccharide or itsderivatives as said organic material, in particular amonosaccharide-polyol advantageously selected from mannitol, erythritol,xylitol, sorbitol and mixtures thereof, preferably mannitol.

Preferably the layered coating surrounding said core comprises at leastone hydrophilic polymer(s) selected from the group consisting ofpolysaccharides and derivatives, preferably the ones including one typeof ose or several type of ose(s), preferably several type of ose(s)including at least D-glucose units, in particular starch andderivatives, cellulose or derivatives, and more preferably starch andderivatives.

Preferably, the microcapsules include at least one lipid based material,preferably with amphiphilic properties such as lecithins and inparticular hydrogenated lecithin.

Advantageously the core represents from 1% to 50% by weight, preferably5 to 30% by weight, and in particular from 10 to 20% by weight relativeto the total weight of the microcapsule.

Advantageously, the colorant(s) represent from 20% to 90%, preferablyfrom 30% to 80%; in particular from 50% to 75% by weight relative to themicrocapsule.

Advantageously, the microcapsules have a size of from 50 μm to 800 μm,in particular from 60 μm to 600 μm, and in particular from 80 μm to 500μm, and in particular from 100 μm to 400 μm.

Particularly, the changing colour gel composition according to theinvention comprises microcapsules comprising at least:

-   -   a inner core made of monosaccharide-polyol, preferably mannitol,    -   at least two layers of different colour,    -   at least one hydrophilic polymer preferably selected from        polysaccharide or derivatives, and more preferably from starch        or derivatives,    -   and advantageously at least one lipid based material, preferably        an amphiphilic compound, more preferably a phospholipid, even        more preferably phosphoacylglycerol such as hydrogenated        lecithin.

Preferably the microcapsules containing releasable colorant(s) aremulti-layered microcapsules containing releasable colorant(s), saidmicrocapsules comprising:

-   -   an uncoloured core consisting in one organic material, and    -   a multi-layered coating surrounding said core and comprising at        least one organic inner layer and one organic outer layer of        different colour and entrapping respectively at least one        colorant.        Preferably the gel is transparent or translucent.

Particularly the changing colour gel composition according to theinvention comprises at least one hydrophilic gelifying agent chosen fromwater-soluble or water dispersible polymers, preferably chosen from:

-   -   modified or unmodified carboxyvinyl polymers;    -   polyacrylates;    -   polymethacrylates;    -   polyacrylamides; optionally crosslinked and/or neutralized        2-acrylamido-2-methylpropanesulfonic acid polymers and        copolymers;    -   crosslinked anionic copolymers of acrylamide and of AMPS;    -   polysaccharide biopolymers, for instance xanthan gum, guar gum,        carob gum, acacia gum, scleroglucans, chitin and chitosan        derivatives, carrageenans, gellans, alginates,    -   celluloses such as microcrystalline cellulose,        carboxymethylcellulose, hydroxymethylcellulose and        hydroxypropylcellulose;    -   and mixtures thereof.

More preferably, the water-soluble or water dispersible polymers ischosen from Acrylates/C10-30 Alkyl Acrylate Crosspolymer; Ammoniumacryloyldimethyl Taurate/Steareth-8 Methacrylate copolymer; Acrylatescopolymer; Ammonium acryloyldimethyl taurate/steareth-25 MethacrylateCrosspolymer; Ammonium acryloyldimethyl taurate such, and xanthan gum.

Advantageously, in the gel composition, the hydrophilic gelifyingagent(s) are in an amount ranging from 0.001 to 10% by weight,preferably 0.01 to 5% by weight and more preferably from 0.05 to 3% byweight relative to the total weight of the composition.

Particularly, the changing composition further comprises one or morewater soluble emollient(s) and/or lipid(s) with a polar moiety.

Particularly, the changing colour gel composition further comprises oneor more solubilizers of water soluble emollient(s), preferably chosenfrom Polysorbate 20, PEG-60 hydrogenated castor oil.

The invention is also directed to a cosmetic process for caring forand/or making up keratinic materials, comprising application on saidkeratinic materials in particular on the skin of a gel composition asdefined according to the invention.

The composition according to the invention, which is preferably a makeupfoundation, provides a very strong moisturizing sensation,advantageously a totally transparent and cleaning bulk appearance withvery comfortable feeling during application, and sheer natural makeupresult after application. At the end, all these characters help delivera very good balance of skincare efficacy perception (watery,moisturization and transparent) as well as makeup efficacy (propercovering effect).

In particular, the technical problem underlying the present inventionhas been solved by using a specific microcapsule wherein pigment can bevery well encapsulated with colorful and clean appearance.

Particularly transparent or slightly colored gels with coloredmicrocapsules homogenously dispersed are advantageously obtained.

DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram illustrating a typical structure of acolor-changing microcapsule of the present invention, wherein Arepresents a core and B, C, D and E being different layersconcentrically surrounding said core.

FIGS. 2 to 10 represent a schematic diagram showing the core-shellstructure of color-changing microcapsules prepared according to Examples6 to 14, respectively, which are described later in this description.

MORE DETAILED DESCRIPTION

The term “physiologically acceptable medium” is intended to denote amedium that is particularly suitable for applying a product of theinvention to keratin materials, especially the skin and moreparticularly facial skin.

The “physiologically acceptable medium” comprises the aqueous phase usedaccording to the present invention.

The word “capsule” is also used to mention “microcapsule”.

For the purposes of the present invention, the term “keratin material”is intended to cover the skin, mucous membranes such as the lips, thenails and the eyelashes. The skin and the lips, in particular facialskin, are most particularly considered according to the invention.

As emerges from the examples that follow, compositions in accordancewith the invention prove to be advantageous in several aspects.

Encapsulation of the colorants prevents undesirable re-agglomeration ofpigments during manufacture and prolonged storage of the cosmeticcompositions.

As the microcapsules of the invention have the ability of swelling orsoftening in contact of an aqueous phase as defined hereunder, they areadvantageously deformable when applied on a keratin material andconsequently provide a soft feeling to the user. Furthermore, their lowsize contributes to not create any discomfort or unfavourable, grainy,feeling when applied.

However, the microcapsules of the invention are soft enough to ruptureupon very slight rubbing or pressing on the skin in order to releasetheir content but, nevertheless, are durable enough to avoid destructionof the coating during manufacture, even during an industrial process,and storage of corresponding change-color composition.

In addition, the microcapsule of the invention allows the use of regularequipment for the preparation of the compositions of the inventionbecause no coloring of the apparatus occurs during the manufacturingprocess.

Accordingly, the microcapsules of the present invention are particularlyinteresting since they mask the original color of the encapsulatedcolorants, increase the stability of these colorants againstdegradation, and prevent undesirable release of the encapsulatedcolorants into the composition during the manufacturing process andprolonged storage.

At last, compositions of the invention also have the advantage ofsatisfying a consumer expectation in terms of cosmetic products.

According to another of its aspects, a subject of the present inventionis also directed to a cosmetic process comprising at least the stepsconsisting in applying at least part of a gel composition according tothe invention on the surface of a keratin material, in particular theskin.

According to the invention, the “color changing composition” means acomposition wherein the color before application is different from thecolor after application, this difference being visible to the nakedeyes.

In particular, this color changing composition may be linked to acolor-difference ΔE in CIE Lab system 1976 (ΔE before/after application)value.

The ΔE is defined by the equation:ΔE*=√{square root over (((L ₁ −L ₂)²+(a ₁ −a ₂)²+(b ₁ −b ₂)²)},wherein L₁, a₁, b₁ are the parameters in the colorimetric space of the1st color (composition before application) and L₂, a₂, b₂ the ones forthe 2^(nd) color (composition after the application and homogenizationon the keratinic material).

These values may be measured by spectrophotometer or with aChrosmasphere (for composition applied on skin).

The color changing composition according to the invention may becharacterized as having a ΔE before/after application superior to 1, inparticular superior or equal to 2, preferably superior or equal to 3.

Coloring Microcapsules

The term “microcapsule”, as used herein, refers to a sphericalmicrocapsule containing at least one layered coating entrapping at leastone colorant and surrounding a core chemically different from thecoating. Microcapsules are distinct from microspheres, which consist ofspherical homogeneous matrix.

According to an embodiment, the “at least one layered coating” is amulti-layered coating preferably an organic multi-layered coating.

The term “multi-layer microcapsule” refers to a microcapsule consistingof a core surrounded by a coating based on one or more inner layer(s)and one outer layer. The one or more inner layer(s) forming themulti-layer coating of the multi-layer microcapsule and the single outerlayer of the microcapsule may be formed of the same or differentwall-forming organic compound(s).

The microcapsule according to the invention comprises a core also called“inner core” surrounded by a coating based on one or more layer(s). In apreferred embodiment, the microcapsule is a ‘multi-layers’ microcapsule,comprising at least one inner layer and one outer layer. The one or moreinner layer(s) forming the multi-layer coating of the multi-layermicrocapsule and the single outer layer of the microcapsule may beformed of the same or different wall-forming organic compound(s).

In a particular embodiment the inner layer and the outer layer areformed of the same wall forming organic compounds, the core is thensurrounded by a one layer coating.

In one embodiment, the outer layer does not comprise any colorant. Inanother embodiment, the outer layer comprises at least one colorant.

The term “wall-forming organic compound” refers to an organic compoundor a combination of two or more different organic compounds as definedherein, which form a component of the layer(s) of the microcapsules. Ina preferred embodiment, the ‘wall-forming organic compound’ comprises atleast one polymer.

The term “colorant” refers to organic pigments such as synthetic ornatural dyes selected from any of the well known FD&C or D&C dyes,inorganic pigments such as metal oxides, or lakes and any combination(blend) thereof. Accordingly, the colorant useful according to thepresent invention may be oil-soluble or oil-dispersible or with limitedsolubility in water.

In preferred embodiments, the colorant is an inorganic pigment, morepreferably a metal oxide.

Generally, average particle sizes of up to about 800 μm in diameter ofcolorant microcapsules are used according to the invention. Preferablythe average particle size is less than about 400 μm in diameter of thecolorant microcapsules for skin care applications. Advantageously theaverage particle size is in the range of about 10 μm to 350 μm indiameter. Preferably, the average particle size will be from 50 μm to800 μm, in particular from 60 μm to 600 μm, and in particular from 80 μmto 500 μm, and in particular from 100 μm to 400 μm in diameter.

In particular, the average particle size may be from 50 to 1000 Mesh(around 400 μm to 10 μm), in particular from 60 to 200 Mesh (around 250μm to 75 μm) as measured by the sieving test method or observed bymicroscope.

Preferably, a composition according to the invention may comprise from0.1% to 20% by weight and preferably from 0.5% to 15% by weight ofmicrocapsules relative to the total weight of the said composition.

In particular for a skin care composition according to the invention,the amount of microcapsules will range from 0.1% to 5%, preferably from0.2% to 3% by weight relative to the total weight of composition.

In particular for a make-up composition according to the invention, theamount of microcapsules will range from 0.5% to 20%, preferably from 1%to 15%, more preferably from 2% to 10% by weight relative to the totalweight of composition.

According to a particular embodiment, the encapsulated colorant(s) maybe present in a composition according to the invention in an amount inactive matter of encapsulated pigments ranging from 0.5% to 20% byweight, in particular from 1% to 15% by weight, and more particularlyfrom 2% to 12% by weight, of the total weight of said composition.

The microcapsules will be integrated in the cosmetic formula generallyat the latest stages of the formulation and after filtering stages ifany, to avoid the microcapsules being broken. Preferably, themicrocapsules according to the inventions are added and mixed uniformlyat temperatures under 50° C. They are mixed gently with a paddle ratherthan a homogenizer.

The microcapsules may be produced by several methods known to the manskilled in the art within the coating or encapsulation domain, includingpelletization, granulation, coating, etc. For example, the microcapsulesmay be obtained by a method comprising mixture of the compounds(actives, pigments, polymers, solvents) and drying to form capsules asdisclosed in WO01/35933 and WO2011/027960, or a method comprisinggranulation and coating by spray drying as disclosed in FR2841155, or byfluidized bed technology, which has been used in the food andpharmaceutical industry for a long time for coating and encapsulatingingredients. As an example may be cited WO2008/139053, which concernsthe preparation of spheroid multilayer capsules comprising a core ofsugar and concentric layers of pharmaceutical actives. Fixation ofpharmaceutical actives on the core is achieved by impregnation,pulverization or projection, and then the 1^(st) layer is dried beforeapplication of a second one.

Fluid bed process is disclosed for example in Teunou et al. (Fluid-BedCoating, Poncelet, 2005, D. Food Science and Technology (Boca Raton,Fla., United States), Volume 146 Issue Encapsulated and Powdered Foods,Pages 197-212). A specific feature of the fluid bed process is that itleads to coated particles wherein the core is well encapsulated,compared to spray drying, which leads to a matrix with the core materialrandomly dispersed in a polymer.

In a preferred embodiment, the microcapsules are obtained by fluid bedprocess.

According to this embodiment, preferably at least one layer of themicrocapsules is obtained by fluid bed process.

In a particular embodiment, the outer layer is obtained by fluid bedprocess.

In another particular embodiment at least one inner layer is obtained byfluid process.

Most preferably, all layers are obtained by fluid bed process.

A man skilled in the art knows how to adjust air quantity, liquidquantity and temperature allowing to reproduce a capsule according tothe invention.

Preferably a fluid bed process implemented according to the inventionincludes Würster process and/or tangential spray process. Such a processallows, contrary to a pelletization process, to prepare sphericalcapsules with a core surrounded by one or more circumferential layers.

When the whole process for preparing the layers surrounding the core ofthe microcapsules according to the invention is carried out by fluid bedprocess, the microcapsule layers are advantageously regular, concentricand present a homogenous thickness.

Different examples of preparation of capsules according to the inventionwill be given later in this description.

I a) Core

The core is made of at least an organic material. The size of said corepreferably ranges from 500 nm to 150 μm in diameter.

Preferably the core is in a solid and/or crystal form at roomtemperature.

In a particular embodiment, the organic material is selected fromorganic materials having high water dissolvability. Preferably, the coreis water-soluble or water-dispersible.

In a particular embodiment, the core is uncoloured, i.e. it does notcontain colorant material.

In a particular embodiment, the core is based on only one compound. Thiscompound is organic and more preferably is a natural compound.

According to a preferred embodiment, the core is sugar-alcohol,preferably a monosaccharide-polyol advantageously selected frommannitol, erythritol, xylitol, sorbitol.

In a particular embodiment, the core is made of mannitol and morepreferably exclusively made of mannitol.

According to an alternative embodiment, the core contains at leastmannitol and at least one additional ingredient being preferably apolymer selected from hydrophilic polymers. In particular, such a coremay comprise mannitol and hydrophilic polymers chosen among cellulosepolymers, starch polymers and their mixture, preferably their mixture.

In a preferred embodiment, the cellulose polymer is acarboxymethylcellulose and the starch polymer is a non-modified naturalstarch, for example corn starch.

The core may be constituted by a seed (or crystal) of one of theprevious materials.

The core is preferably contained in an amount of from 1% to 50% byweight, preferably 4 to 40% by weight, in particular 5 to 30% by weight,and in particular from 10 to 20% by weight with respect to the totalweight of the micro capsule.

The mannitol is preferably contained in an amount of from 2% to 100% byweight, preferably 5 to 100% by weight, and in particular 100% by weightwith respect to the total weight of the core.

The mannitol is preferably contained in an amount of from 1% to 50% byweight, preferably 4% to 40% by weight, in particular 5% to 30% byweight, and in particular from 10% to 20% by weight with respect to thetotal weight of the microcapsule.

I b) External Layer(s) or Coating

As disclosed previously, the core is advantageously surrounded with acoating, or external layer(s) preferably comprising at least one innerlayer and one outer layer. In this latter case, these layers preferablyextend concentrically in respect with the core.

The layer(s) is/are preferably organic, i.e. contain(s) at least oneorganic compound as wall-forming material. Preferably, the inner and/orouter layer(s) include(s) at least one polymer, and in particular ahydrophilic polymer.

Polymer(s)

The composition according to the invention comprises one or morepolymer(s). In a particular embodiment, the polymer(s) is/arehydrophilic polymer(s).

Such hydrophilic polymer(s) is/are soluble or dispersible in water or inalcohol compounds, in particular chosen from lower alcohols, glycols,polyols.

For the purposes of the present patent application, the term“hydrophilic polymer” means a (co)polymer that is capable of forminghydrogen bond(s) with water or alcohol compounds, in particular chosenfrom lower alcohols, glycols, polyols. In particular, polymers areconcerned which are capable of forming O—H, N—H and S—H bonds.

According to a particular embodiment of the invention, the hydrophilicpolymer may swell or soften in contact with water or alcohol compounds,in particular chosen from lower alcohols, glycols, polyols.

The hydrophilic polymer(s) may be chosen from the following polymer(s):

-   -   acrylic or methacrylic acid homopolymers or copolymers or salts        and esters thereof and in particular the products sold under the        names Versicol F or Versicol K by the company Allied Colloid,        Ultrahold 8 by the company Ciba-Geigy, and polyacrylic acids of        Synthalen K type, and salts, especially sodium salts, of        polyacrylic acids (corresponding to the INCI name sodium        acrylate copolymer) and more particularly a crosslinked sodium        polyacrylate (corresponding to the INCI name sodium acrylate        copolymer (and) caprylic/capric triglycerides) sold under the        name Luvigel EM by the company;    -   copolymers of acrylic acid and of acrylamide sold in the form of        the sodium salt thereof under the names Reten by the company        Hercules, the sodium polymethacrylate sold under the name Darvan        No. 7 by the company Vanderbilt, and the sodium salts of        polyhydroxycarboxylic acids sold under the name Hydagen F by the        company Henkel;    -   polyacrylic acid/alkyl acrylate copolymers, preferably modified        or unmodified carboxyvinyl polymers; the copolymers most        particularly preferred according to the present invention are        acrylate/C₁₀-C₃₀-alkylacrylate copolymers (INCI name:        Acrylates/C₁₀₋₃₀ Alkyl acrylate Crosspolymer) such as the        products sold by the company Lubrizol under the trade names        Pemulen TR1, Pemulen TR2, Carbopol 1382 and Carbopol ETD 2020,        and even more preferentially Pemulen TR-2;    -   alkylacrylic/alkylmethacrylic acid copolymers and their        derivatives notably their salts and their esters, such as the        copolymer of ethyl acrylate, methyl methacrylate and low content        of methacrylic acid ester with quaternary ammonium groups        provided under the tradename of EUDRAGIT RSPO from Evonik        Degussa;    -   AMPS (polyacrylamidomethylpropanesulfonic acid partially        neutralized with aqueous ammonia and highly crosslinked) sold by        the company Clariant;    -   AMPS/acrylamide copolymers such as the products Sepigel or        Simulgel sold by the company SEPPIC, especially a copolymer of        INCI name Polyacrylamide (and) C13-14 Isoparaffin (and)        Laureth-7;    -   polyoxyethylenated AMPS/alkyl methacrylate copolymers        (crosslinked or non-crosslinked) of the type such as Aristoflex        HMS sold by the company Clariant;    -   polysaccharides and derivatives, such as:        -   anionic, cationic, amphoteric or nonionic chitin or chitosan            polymers;        -   cellulose polymers and derivatives, preferably other than            alkylcellulose, chosen from hydroxyethylcellulose,            hydroxypropylcellulose, hydroxymethylcellulose,            ethylhydroxyethylcellulose and carboxymethylcellulose, and            also quaternized cellulose derivatives; in a preferred            embodiment, the cellulose polymers is a            carboxymethylcellulose;        -   Starch polymers and derivatives, eventually modified; in a            preferred embodiment, the starch polymer is a natural            starch;        -   optionally modified polymers of natural origin, such as            galactomannans and derivatives thereof, such as konjac gum,            gellan gum, locust bean gum, fenugreek gum, karaya gum, gum            tragacanth, gum arabic, acacia gum, guar gum, hydroxypropyl            guar, hydroxypropyl guar modified with sodium            methylcarboxylate groups (Jaguar XC97-1, Rhodia),            hydroxypropyltrimethylammonium guar chloride, and xanthan            derivatives;        -   alginates and carrageenans;        -   glycoaminoglycans, hyaluronic acid and derivatives thereof;        -   mucopolysaccharides such as hyaluronic acid and chondroitin            sulfates, and mixtures thereof;    -   vinyl polymers, for instance polyvinylpyrrolidones, copolymers        of methyl vinyl ether and of malic anhydride, the copolymer of        vinyl acetate and of crotonic acid, copolymers of        vinylpyrrolidone and of vinyl acetate; copolymers of        vinylpyrrolidone and of caprolactam; polyvinyl alcohol;

and the mixtures thereof.

Preferably, the composition according to the invention, and inparticular the external layer(s) comprise(s) hydrophilic polymersselected from the group consisting of polysaccharides and derivatives,acrylic or methacrylic acid homopolymers or copolymers or salts andesters thereof, and their mixture.

The said polymer(s) is (are) advantageously selected from(poly)(alkyl)(meth)acrylic acid and derivatives, notably(poly)(alkyl)(meth)acrylate and derivatives, preferably fromalkylacrylic/alkylmethacrylic acid copolymers and their derivatives, andmost preferably is a copolymer of ethyl acrylate, methyl methacrylateand low content of methacrylic acid ester with quaternary ammoniumgroups provided under the tradename of EUDRAGIT RSPO from EvonikDegussa.

Said polysaccharides and derivatives are preferably selected fromchitosan polymers, chitin polymers, cellulose polymers, starch polymers,galactomannans, alginates, carrageenans, mucopolysaccharides, and theirderivatives, and the mixture thereof.

In a preferred embodiment, the external layer(s) is/are devoid ofmicrocrystalline cellulose.

According to one particularly preferred embodiment, said polysaccharidesand their derivatives are preferably selected from the ones includingone type of ose or several type of ose(s), preferably several types ofoses, in particular at least D-Glucose unit(s) as ose(s), preferablystarch polymers, cellulose polymers, and derivatives, and the mixturethereof.

According to a preferred embodiment, the microcapsule contains at leastone hydrophilic polymer selected from the group consisting of starch andits derivatives, in particular corn starch, cellulose and itsderivatives, homo- and/or co-polymer of methacrylic acid and/ormethacrylic acid ester or co-polymer of (alkyl)acrylic acid and/or(alkyl)methacrylic acid and their derivatives, preferably their saltsand their ester, and in particular the capsule contains polymethylmethacrylate.

Starch usable according to the present invention is usually issued fromvegetable raw materials, such as rice, soybeans, potatoes, or corn.Starch can be unmodified or (by analogy with cellulose) modified starch.In a preferred embodiment, the starch is unmodified.

Preferred homo- and/or co-polymer of methacrylic acid and/or methacrylicacid ester are those wherein the copolymer of methyl methacrylate andethyl acrylate has a molecular weight from 750 to 850 kDa.

Cellulose derivatives include, for example, alkali cellulosescarboxymethyl cellulose (CMC), cellulose esters and ethers, andaminocelluloses. In a particular embodiment, the cellulose is acarboxymethyl cellulose (CMC).

According to a preferred embodiment, the capsule contains at leaststarch derivative, in particular corn starch, polymethyl methacrylate,co-polymer of (alkyl)acrylic acid and/or (alkyl)methacrylic acid andtheir derivatives preferably their salts and their ester, and/orcellulose derivative.

Preferably, the microcapsule contains polymer(s) which are notcross-linked.

The polymer(s) may be in one or several layer(s).

In another embodiment, the polymer(s) may be in the core.

The microcapsule may contain polymer(s) in the core and/or in thelayer(s).

In a particular embodiment, the polymer(s) is (are) in the core and inthe layer(s).

In an embodiment, the core contains at least starch and/or cellulosederivative as polymer(s). When the starch is contained within the core,it represents the main ingredient of such a core, i.e. the weight amountof starch is greater than the respective amount of other compounds ofthe core.

The polymer may represent from 0.5 to 20% by weight of the microcapsule,in particular from 1 to 10% by weight, preferably from 2 to 8% by weightof the microcapsule.

The different layers forming the coating may be based on identical ordifferent polymers. Advantageously, they will be formed from the samepolymer.

In contrast, the layers will be advantageously differently coloured.

This different colour may be obtained through the use of differentcolorants but also the use of different concentrations in at least onecolorant when the colorant will be the same for two layers.

In a particular embodiment, the outer layer contains at least onecolorant.

In another embodiment, the outer layer does not contain any colorant.

Colorant(s)

As previously stated, “colorant” includes any organic or inorganicpigment or colorant approved for use in cosmetics by CTFA and the FDAused in cosmetic formulations.

Thus the term “colorant” refers to organic pigments such as synthetic ornatural dyes selected from any of the well known FD&C or D&C dyes, toinorganic pigments such as metal oxides, or lakes such as the ones basedon cochineal carmine, barium, strontium, calcium or aluminum and anycombination (blend) thereof. Such colorants are detailed here-after.

In a particular embodiment, the colorant may be water-soluble orwater-dispersible.

In another embodiment, the colorant useful according to the presentinvention may be oil-soluble or oil-dispersible or with limitedsolubility in water.

In preferred embodiments, the colorant is an inorganic pigment, morepreferably a metal oxide.

Advantageously, the colorants of the multi-layer microcapsules areprimary metal oxides selected from iron oxides, titanium dioxide,aluminum oxide, zirconium oxides, cobalt oxides, cerium oxides, nickeloxides, tin oxide or zinc oxide, or composite oxides, more preferably aniron oxide selected from red iron oxide, yellow iron oxide or black ironoxide, or a mixture thereof.

The layer(s) may also contain lakes corresponding to an organic colorantsecured to a substrate. Such (a) lake(s) is (are) advantageously chosenamong the here-below material, and their mixture(s):

-   -   carmin of cochineal;    -   organic pigments of azoic, anthraquinonic, indigoid, xanthenic,        pyrenic, quinolinic, triphenylmethane, fluoran colorants; Among        the organic pigments may be cited those known under the        following trademark references: D&C Blue no 4, D&C Brown no 1,        D&C Green no 5, D&C Green no 6, D&C Orange no 4, D&C Orange no        5, D&C Orange no 10, D&C Orange no 11, D&C Red no 6, D&C Red no        7, D&C Red no 17, D&C Red no 21, D&C Red no 22, D&C Red no 27,        D&C Red no 28, D&C Red no 30, D&C Red no 31, D&C Red no 33, D&C        Red no 34, D&C Red no 36, D&C Violet no 2, D&C Yellow no 7, D&C        Yellow no 8, D&C Yellow no 10, D&C Yellow no 11, FD&C Blue no 1,        FD&C Green no 3, FD&C Red no 40, FD&C Yellow no 5, FD&C Yellow        no 6;    -   the water-insoluble salts of sodium, potassium, calcium, baryum,        aluminum, zirconium, strontium, titanium, of acid colorants such        as azoic, anthraquinonic, indigoids, xanthenic, pyrenic,        quinolinic, triphenylmethane, fluoran colorants, these colorants        may include at least one carboxylic or sulfonic acid group.

The organic lakes may also be protected by an organic support such asrosin or aluminum benzoate.

Among the organic lakes, we may in particular cite those known under thefollowing names: D&C Red no 2 Aluminum lake, D&C Red no 3 Aluminum lake,D&C Red no 4 Aluminum lake, D&C Red no 6 Aluminum lake, D&C Red no 6Barium lake, D&C Red no 6 Barium/Strontium lake, D&C Red no 6 Strontiumlake, D&C Red no 6 Potassium lake, D&C Red no 6 Sodium lake, D&C Red no7 Aluminum lake, D&C Red no 7 Barium lake, D&C Red no 7 Calcium lake,D&C Red no 7 Calcium/Strontium lake, D&C Red no 7 Zirconium lake, D&CRed no 8 Sodium lake, D&C Red no 9 Aluminum lake, D&C Red no 9 Bariumlake, D&C Red no 9 Barium/Strontium lake, D&C Red no 9 Zirconium lake,D&C Red no 10 Sodium lake, D&C Red no 19 Aluminum lake, D&C Red no 19Barium lake, D&C Red no 19 Zirconium lake, D&C Red no 21 Aluminum lake,D&C Red no 21 Zirconium lake, D&C Red no 22 Aluminum lake, D&C Red no 27Aluminum lake, D&C Red no 27 Aluminum/Titanium/Zirconium lake, D&C Redno 27 Barium lake, D&C Red no 27 Calcium lake, D&C Red no 27 Zirconiumlake, D&C Red no 28 Aluminum lake, D&C Red no 28 Sodium lake D&C Red no30 lake, D&C Red no 31 Calcium lake, D&C Red no 33 Aluminum lake, D&CRed no 34 Calcium lake, D&C Red no 36 lake, D&C Red no 40 Aluminum lake,D&C Blue no 1 Aluminum lake, D&C Green no 3 Aluminum lake, D&C Orange no4 Aluminum lake, D&C Orange no 5 Aluminum lake, D&C Orange no 5Zirconium lake, D&C Orange no 10 Aluminum lake, D&C Orange no 17 Bariumlake, D&C Yellow no 5 Aluminum lake, D&C Yellow no 5 Zirconium lake, D&CYellow no 6 Aluminum lake, D&C Yellow no 7 Zirconium lake, D&C Yellow no10 Aluminum lake, FD&C Blue no 1 Aluminum lake, FD&C Red no 4 Aluminumlake, FD&C Red no 40 Aluminum lake, FD&C Yellow no 5 Aluminum lake, FD&CYellow no 6 Aluminum lake.

The chemistry material corresponding to each of these organic colorantspreviously cited are mentioned in the book called <<InternationalCosmetic Ingredient Dictionary and Handbook>>, Edition 1997, pages 371to 386 and 524 to 528, published by <<The Cosmetic, Toiletry, andFragrance Association>>, of which the content is hereby incorporated byreference in the present specification.

According to a preferred embodiment, the lake(s) is/are selected fromcarmin of cochineal and the water-insoluble salts of sodium, potassium,calcium, barium, aluminum, zirconium, strontium, titanium, of acidcolorants such as azoic, anthraquinonic, indigoid, xanthenic, pyrenic,quinolinic, triphenylmethane, fluoran colorants, being given that thesecolorants may include at least one carboxylic or sulfonic acid group,and their mixture.

According to a preferred embodiment, the lake(s) is/are selected fromcarmin of cochineal and the water-insoluble salts of sodium, calcium,aluminum, and their mixture.

As lake incorporating carmine we may cite the commercial references:CARMIN COVALAC W 3508, CLOISONNE RED 424C et CHROMA-LITE MAGENTA CL4505.

The water-insoluble aluminum salts are preferably selected from FDCYellow No 5 aluminum lake, le FDC Blue No 1 aluminum lake, le FDC Red No40 aluminum lake, le FDC Red No 30 aluminum lake, le FDC Green No 5aluminum lake, and their mixtures. As compound incorporating suchinorganic lake may notably be cited the commercial references: INTENZAFIREFLY C91-1211, INTENZA AZURE ALLURE C91-1251, INTENZA THINK PINKC91-1236

The water-insoluble calcium salts are preferably selected from Red No 7calcium lake. As compound incorporating such inorganic lake may notablybe cited the commercial references: INTENZA MAGENTITUDE C91-1234,INTENZA HAUTE PINK C91-1232, INTENZA RAZZLED ROSE C91-1231, INTENZAAMETHYST FORCE C91-7231, INTENZA PLUSH PLUM C91-7441, INTENZA ELECTRICCORAL C91-1233, FLORASOMES-JOJOBA-SMS-10% CELLINI RED-NATURAL and theirmixture.

The water-insoluble sodium salts are preferably selected from Red No 6sodium lake and Red No 28 sodium lake, and their mixture. E As compoundincorporating such inorganic lake may notably be cited the commercialreferences: INTENZA MANGO TANGO C91-1221 et INTENZA NITRO PINK C91-1235.

In preferred embodiments, the colorant is an inorganic colorant.

In a preferred embodiment, the colorant is a metallic oxide. Suchmetallic oxide is preferably selected from iron oxides, titanium oxides,and mixtures thereof.

The color-changing compositions of the invention may comprise a mixtureof two or more colorants, either encapsulated individually inmicrocapsules and/or one or more blends of colorants encapsulated withinthe multi-layer microcapsules.

In accordance with this specific embodiment, each layer of themicrocapsule may contain at least one specific colorant or a specificblend of colorant(s).

In accordance with this specific embodiment, the color-changingcomposition of the invention comprises two or more microcapsules of theinvention having different colors.

A person skilled in the art knows how to choose colorants andcombinations of colorants to produce a desired color effect or colorchange.

As stated previously, the microcapsules of the invention containpreferably at least titanium dioxide and/or iron oxides in theircoating, preferably at least titanium dioxide.

In a preferred embodiment, the microcapsules of the invention containpreferably at least titanium dioxide and iron oxides in their coating.

According to a specific embodiment, the outer layer of saidmicrocapsules contains titanium dioxide and more preferably as onlycolorant.

According to these specific embodiments, the outer layer of saidmicrocapsules contains titanium dioxide as the sole colorant and thecomposition according to the invention is non-colored, “non-colored” or“uncolored” composition meaning a transparent or white composition.

According to a preferred embodiment the composition according to thepresent invention, comprises uncoloured microcapsules, that is the outerlayer being white or transparent, and when the outer layer istransparent, the visible inner layer is white.

For the purposes of the invention, the term “transparent composition”means a composition which transmits at least 40% of light at awavelength of 750 nm without scattering it, i.e. a composition in whichthe scattering angle of the light is less than 5° and is better stillabout 0°.

The transparent composition may transmit at least 50%, especially atleast 60% and especially at least 70% of light at a wavelength of 750nm.

The transmission measurement is made with a Cary 300 Scan UV-visiblespectrophotometer from the company Varian, according to the followingprotocol:

-   -   the composition is poured into a square-sided spectrophotometer        cuvette with a side length of 10 mm;    -   the sample of the composition is then maintained in a        thermostatically-regulated chamber at 20° C. for 24 hours;    -   the light transmitted through the sample of the composition is        then measured on the spectrophotometer by scanning wavelengths        ranging from 700 nm to 800 nm, the measurement being made in        transmission mode;    -   the percentage of light transmitted through the sample of the        composition at a wavelength of 750 nm is then determined.

The transparent compositions, when they are placed 0.01 m in front of ablack line 2 mm thick in diameter drawn on a sheet of white paper, allowthis line to be seen; in contrast, an opaque composition, i.e. anon-transparent composition, does not allow the line to be seen.

According to a specific embodiment, the outer layer of saidmicrocapsules contains organic pigments or iron oxides.

The colorants are present in amounts ranging from 20% to 90% by weight,preferably from 30% to 80% by weight, more preferably from 50% to 75% byweight relative to the total weight of the microcapsule.

In a particular embodiment, the microcapsules contain metallic oxidesselected from iron oxides, titanium oxides, and mixtures thereof,present in an amount ranging from 20% to 90% by weight, preferably from30% to 85% by weight, more preferably from 50% to 85% by weight relativeto the total weight of the microcapsule.

In particular the titanium oxide may be present from 28% to 80% byweight, preferably from 30% to 75% by weight, and more preferably from30 to 50% by weight, relative to the total weight of the microcapsule.

In particular the iron oxides may be present from 5% to 75% by weight,preferably 8% to 65% by weight relative to the total weight of themicrocapsule. In a particular embodiment, the iron oxides are present inan amount higher than 15% by weight, preferably higher than 30% byweight, and in particular from 40% to 65% by weight relative to thetotal weight of the microcapsule.

In a preferred embodiment, in at least one layer, and preferably inevery layer, the colorants are the main ingredients, i.e. represent atleast 40% by weight of the layer(s), preferably at least 75% by weightof the layer(s), more preferably at least 95% by weight of the layer(s).

In a preferred embodiment the mean thickness of the titanium dioxidelayer ranges from 5 μm to 150 μm.

Lipid-Based Material

The inner and/or outer layer(s) may also include advantageously at leastone lipid-based material.

According to a particular embodiment of this invention, such alipid-based material may have amphiphilic properties, that is to sayhaving an apolar part and a polar part.

Such lipid-based material can include at least one or several C₁₂-C₂₂fatty acid chain(s) such as those selected from stearic acid, palmiticacid, oleic acid, linoleic acid, linolenic acid, etc., and mixturesthereof. Preferably these fatty acids chains are hydrogenated.Eventually, these fatty acid chains may be the apolar part of alipid-based material.

Such lipid-based material is preferably selected from phospholipids.These phospholipids are preferably selected from phosphoacylglycerol,more preferably selected from lecithins, and are in particularhydrogenated lecithin.

The lipid based material may represent from 0.05 to 5% by weight of themicrocapsule, in particular from 0.1 to 1% by weight of microcapsule.

By combining three or more compounds (ex: sugar alcohols, polymers,lipid-based material) in the microcapsule of different hardness and/orwater solubility, it is possible to adjust the time required forcolorant-encapsulated microcapsules to break down on the skin so that,by varying the method or intensity of application onto the skin, it ispossible to adjust the preferred colouration or gradation pattern.

Thus, according to a preferred embodiment, the multi-layer coatingcontains at least starch as polymer and at least one lipid-basedmaterial, which is preferably lecithin.

According to an advantageous embodiment the microcapsules according tothe invention include at least one monosaccharide or its derivative andat least one polysaccharide or its derivatives.

According to a preferred embodiment, the microcapsules include a corecomprising a monosaccharide derivative and a coating comprising apolysaccharide (or its derivative) including one type of ose or severaltype of ose(s), preferably several types of oses.

According to a more preferably embodiment, the microcapsules include acore comprising a monosaccharide polyol, preferably selected frommannitol, erythritol, xylitol, sorbitol, and a coating comprising apolysaccharide (or its derivative) including as ose(s) at least one ormore D-Glucose unit(s).

According to a preferred embodiment, the microcapsules include three ormore colorants in different layers.

According to a preferred embodiment, the microcapsules additionallyinclude a lipid-based material chosen from phospholipids, advantageouslyselected from phosphoacylglycerol and in particular from lecithins.

In a particular embodiment, the core contains mannitol, starch polymerand cellulose derivatives and optionally a lipid-based material. In sucha case, the starch polymer is the main ingredient i.e. the weight amountof starch is greater than the respective amount of mannitol, cellulosederivative and lipid-based material of the core.

Referring to FIG. 1, according to a preferred embodiment, the presentinvention advantageously provides a color-changing microcapsule having asize ranging from 50 μm to 800 μm, preferably from 60 μm to 500 μm indiameter of the microcapsule, comprising:

i) a core (A), preferably having a size ranging from 500 nm to 150 μm indiameter, which preferably does not contain any colorant, and comprisingat least one organic core preferably selected from at least one sugaralcohol preferably a monosaccharide-polyol advantageously selected frommannitol, erythritol, xylitol, sorbitol, and mixture thereof;

ii) one first layer (B) surrounding said core comprising:

-   -   at least one colorant, preferably iron oxide(s), and    -   a binder selected from at least one polymer, at least one        lipid-based material, and their mixture, preferably their        mixture;

iii) one second layer (C) surrounding said first layer (B), preferablyhaving a thickness of 5 to 500 μm, comprising:

-   -   titanium dioxide particles, and    -   a binder selected from at least one polymer, at least one        lipid-based material, and their mixture, preferably their        mixture;

iv) optionally one third layer (D) surrounding said second layer (C)comprising:

-   -   at least one colorant, and    -   a binder selected from at least one polymer, at least one        lipid-based material, and their mixture, preferably their        mixture;

v) optionally one fourth layer (E) surrounding said third layer (D), ifany, or surrounding said second layer (C) comprising

-   -   at least one wall-forming polymer preferably selected from        polysaccharides such as cellulose derivatives, in particular        cellulose ether and cellulose ester, from        (poly)(alkyl)(meth)acrylic acid and derivatives, notably        (poly)(alkyl)(meth)acrylate and derivatives, and preferably from        alkylacrylic/alkylmethacrylic acid copolymers and their        derivatives.

As examples of commercially available microcapsules to be used in thecomposition of the invention, we may refer to the followingmicrocapsules produced by Korea Particle Technology KPT under thecommercial names:

-   -   Magic 60-WP0105 from KPT: pink spherical microcapsule containing        titanium dioxide, mannitol, hydrogenated lecithin, synthetic        fluorphlogopite, red 30 lake, zea mays (corn) starch, tin oxide,        having 60-200 Mesh particle size;    -   Magic50-BW0105 from KPT: ash gray spherical microcapsule        containing mannitol, iron oxide red, iron oxide yellow, iron        oxide black, hydrogenated lecithin, titanium dioxide, zea mays        (corn) starch, having 60-200 Mesh particle size.

The microcapsules suitable for the present invention are stable into thecompositions according to the present invention, preferably at hightemperatures, for instance greater than or equal to 40° C., for examplefor one month, better two months and still better three months in anoven at 45° C. or for 15 days in an oven at 60° C.

In a preferred embodiment, the microcapsules according to the presentinvention present an appropriate softening kinetics.

That is preferably, at least three hours after being in contact with theother compounds of the formula, the hardness of the microcapsules isadvantageously from 5 to 50 grams, more preferably from 6 to 20 gramsand still more preferably from 7 to 10 grams. Such hardness is inconformity with an industrial process for preparing the cosmeticcompositions including such microcapsules.

Such values of softening kinetics and hardness allow to provide not onlyaesthetic microcapsules but also overall aesthetic compositions.

Particularly, the composition may lead to different shades or colorgradations depending on the intensity of the rubbing. The compositionsmay advantageously present a high chromaticity C* as measured in the inCIE Lab system 1976.

Gel Formulation

The composition is in the form of a gel and in particular a transparentgel, and comprising from 0.1 to 10% by weight relative to the weight ofthe composition of microcapsules.

Preferably, the viscosity of the gel according to the invention issuperior or equal to 20 UD (Mobile 3) by Rheomat at 25° C.

The viscosity is generally measured at 25° C. with a viscosimeterRHEOMAT RM 180 with Mobile 3 adapted to the viscosity of the product tobe tested (mobile is chosen for having a measure between 10 and 90 forUD Unit Deviation), the measure being made after 10 nm rotating themobile inside the composition, with a cisaillement from 200 s-1. The UDvalues may then be converted in Poises (1 Poise=0.1 Pa·s) with acorrespondence table.

More preferably, the composition contains a gelified aqueous phase.

Hydrophilic gelling agents that may be mentioned in particular includewater-soluble or water-dispersible thickening polymers. These polymersmay be chosen especially from:

-   -   modified or unmodified carboxyvinyl polymers, such as the        products sold under the name Carbopol (CTFA name: Carbomer) by        the company Goodrich; polyacrylates    -   polymethacrylates such as the products sold under the names        Lubrajel and Norgel by the company Guardian or under the name        Hispagel by the company Hispano Chimica;    -   polyacrylamides; optionally crosslinked and/or    -   neutralized 2-acrylamido-2-methylpropanesulfonic acid polymers        and copolymers, for instance the        poly(2-acrylamido-2-methylpropanesulfonic acid) sold by the        company Clariant under the name Hostacerin AMPS (CTFA name:        ammonium polyacryldimethyltauramide);    -   crosslinked anionic copolymers of acrylamide and of AMPS, which        are in the form of a W/O emulsion, such as those sold under the        name Sepigel 305 (CTFA name: Polyacrylamide/C13-14        isoparaffin/Laureth-7) and under the name Simulgel 600 (CTFA        name: Acrylamide/Sodium acryloyldimethyltaurate        copolymer/Isohexadecane/Polysorbate 80) by the company SEPPIC;    -   polysaccharide biopolymers, for instance xanthan gum, guar gum,        carob gum, acacia gum, scleroglucans, chitin and chitosan        derivatives, carrageenans, gellans, alginates,    -   celluloses such as microcrystalline cellulose,        carboxymethylcellulose, hydroxymethylcellulose and        hydroxypropylcellulose; and mixtures thereof. Preferably, these        polymers may be chosen from Acrylates/C10-30 Alkyl Acrylate        Crosspolymer such as, Carbopol ultrez 20, Carbopol ultrez 21,        Permulen TR-1, Permulen TR-2, Carbopol 1382, Carbopol ETD 2020,        Carbomer such as Synthalen K, carbopol 980, Ammonium        acryloyldimethyl Taurate/Steareth-8 Methacrylate copolymer such        as Aristoflex SNC, Acrylates copolymer such as Carbopol Aqua        SF-1, Ammonium acryloyldimethyl taurate/steareth-25 Methacrylate        Crosspolymer such as Aristoflex HMS, Ammonium acryloyldimethyl        taurate such as Arisfoflex AVC, and xanthan gum such as Keltrol        CG, etc, and also any polymers which contribute not only to        sustain a proper viscosity, to further make capsule suspension        very well and further to make it stable in shelf lives, but also        to deliver a transparency.

According to a specific embodiment, the aqueous phase of the compositioncontains at least one neutralized 2-acrylamido-2-methylpropanesulfonicacid polymers and copolymers and one polysaccharide biopolymer.

Preferably, the hydrophilic gelifying agents suitable in the presentinvention include carboxyvinyl polymers such as the Carbopol products(carbomers) such as Carbopol Ultrez 20 Polymer® marketed by Lubrizol andthe Pemulen products (acrylate/C₁₀-C₃₀-alkylacrylate copolymer);polyacrylamides, for instance the crosslinked copolymers marketed underthe trademarks Sepigel 305 (CTFA name: polyacrylamide/C₁₃₋₁₄isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodiumacryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) bySEPPIC; 2-acrylamido-2-methylpropanesulfonic acid polymers andcopolymers, which are optionally crosslinked and/or neutralized, forinstance the poly(2-acrylamido-2-methylpropanesulfonic acid) marketed byHoechst under the trademark Hostacerin AMPS (CTFA name: ammoniumpolyacryloyldimethyltaurate) or Simulgel 800 marketed by SEPPIC(CTFAname: sodium polyacryloyldimethyltaurate/polysorbate 80/sorbitanoleate); copolymers of 2-acrylamido-2-methylpropanesulfonic acid and ofhydroxyethyl acrylate, for instance Simulgel NS and Sepinov EMT 10marketed by SEPPIC; cellulose-based derivatives such ashydroxyethylcellulose; polysaccharides and especially gums such asxanthan gum; and mixtures thereof.

More preferably, the hydrophilic gelifying agent is chosen among anacrylate/C₁₀-C₃₀-alkylacrylate copolymer, carbomer, xanthan gum,carboxyvinylic polymer synthetized in methylene chloride, and ammoniumpolyacryloyldimethyltaurate, and mixtures thereof.

These gelifying agents may be present in an amount ranging for examplefrom 0.001 to 10% by weight, preferably 0.01 to 5% by weight and morepreferably from 0.05 to 3% by weight relative to the total weight ofsaid composition.

More preferably the aqueous gel is transparent.

The expression “transparent aqueous medium” means a medium allowinglight to pass without causing deviation by refraction or reflection. Thetransparency of the aqueous medium can be measured using a turbidimeter.The portable Turbidimeter 2100P® Model from HACH company may be used,for example, for measuring the ranges of transparency of thecomposition. The composition is considered to be transparent when themeasured value of turbidity is between 0 and 250 NTU and is consideredas a translucent for a value of turbidity from 250 to 1000 NTU.

The transparent compositions, when placed in front of a 0.01 m thickblack line with diameter of 2 mm drawn on a white sheet, reveal thisblack line, as opposed to an opaque composition that is to say, nottransparent which would not allow it.

The changing color composition in the form of a transparent gelaccording to the invention preferably comprises water and multi-layeredmicrocapsules containing releasable colorant(s).

In a first preferred embodiment, the transparent gel according to theinvention comprises at least one hydrophilic or lipophilic gelling agentand at least one water soluble emollient(s) and/or lipid(s) with a polarmoiety.

In a first preferred embodiment, the transparent gel according to theinvention comprises at least two types of different multi-layeredmicrocapsules containing releasable colorant(s).

The transparent gel according to the invention, which is preferably a BBproduct or a foundation, provides very strong moisturizing sensation,transparent, cleaning bulk appearance with very comfortable feelingduring application and sheer natural make-up result after application.These features help to deliver both skincare efficacy perception(watery, moisturization and transparent) as well as make-up efficacy(proper coverage).

Advantageously the transparent gel contains a swelling agent, inparticular as disclosed here-after, this agent allows a better swellingof the microcapsules thus rendering the microcapsules easier to breakduring application. Water, alcohols, glycols polyols may be used asswelling agent. Examples of swelling agents are disclosed above.

The moisturization may further be enhanced by introduction of one ormore water soluble emollient(s) and/or lipid(s) with a polar moiety. PEGmodified silane and silicone such as Bis-PEG-18 Methyl ether dimethylsilane, and/or PEG modified ester such as PEG-7 Olivate, PEG-7 GlycerylCocoate, PEG-30 Glyceryl Cocoate, PEG-80 Glyceryl Cocoate, may be usedto enhance moisturization.

A solubilizer may also be added in order to keep the properties of thetransparent gel on storage, in particular to make emollients solubilizedin water phase, to make and keep gel transparent and stable in shelflives. Polysorbate 20, PEG-60 hydrogenated castor oil may be mentionedas examples of solubilizers particularly of solubilizers of the abovementioned water soluble emollient(s).

The transparent gel according to the invention presents a verybeautiful, clean and tidy appearance, with pigments releasing duringapplication without any particle feeling. Makeup results are perfectlyand evenly provided after application.

A preferred embodiment of the transparent gel according to the inventioncomprises:

at least one of the polymers chosen from Acrylates/C10-30 Alkyl AcrylateCrosspolymer such as Permulen TR-1, Permulen TR-2, Carbopol 1382,Carbopol ETD 2020, preferably in a concentration from 0 to 10% wgt, morepreferably from 0 to 2% wgt, Carbomer such as Synthalen K, carbopol 980preferably in a concentration from 0 to 10% wgt, more preferably from 0to 2% wgt, Ammonium acryloyldimethyl Taurate/Steareth-8 Methacrylatecopolymer such as Aristoflex SNC, preferably in a concentration from 0to 10% wgt, more preferably from 0 to 2% wgt, Acrylates copolymer suchas Carbopol Aqua SF-1 preferably in a concentration from 0 to 10% wgt,more preferably from 0 to 2% wgt, Ammonium acryloyldimethyltaurate/steareth-25 Methacrylate Crosspolymer such as Aristoflex HMS,preferably in a concentration from 0 to 10% wgt, more preferably from 0to 2% wgt, Ammonium acryloyldimethyl taurate such as Arisfoflex AVC,preferably in a concentration from 0 to 10% wgt, more preferably from 0to 4% wgt and xanthan gum such as Keltrol CG, preferably in aconcentration from 0 to 10% wgt, more preferably from 0 to 4% wgt.

Moreover the transparent gel may contain at least one of the followingswelling agent, water such as deionized water, preferably in aconcentration from 0 to 90% wgt, more preferably from 30 to 70% wgt,alcohols preferably in a concentration from 0 to 50% wgt, morepreferably from 1 to 20% wgt, glycols such as propyl glycol, butylglycol, preferably in a concentration from 0 to 50% wgt, more preferablyfrom 1 to 15% wgt, polyols such as glycerin, tetraols, preferably in aconcentration from 0 to 50% wgt, more preferably from 1 to 10% wgt.

In addition, the transparent gel may contain at least one water solubleemollients chosen from Bis-PEG-18 Methyl ether dimethyl silane, PEG-7Olivate, PEG-7 Glyceryl Cocoate, PEG-30 Glyceryl Cocoate, PEG-80Glyceryl Cocoate, in a concentration from 0 to 20% wgt, more preferablyfrom 0 to 5% wgt, and at least one solubilizers such as polysorbate 20,PEG-60 hydrogenated castor oil, in a concentration from 0 to 10% wgt,more preferably from 1 to 5% wgt.

Microcapsules such as Magic 60-WP0105, and Magic50-BW0105 from KoreaParticle Technology in a concentration from 0.1 to 10% wgt, morepreferably from 1 to 10% wgt may be introduced at last step with gentlestirring but without side scrapper after gel is made.

In the case of caring composition, the composition according to theinvention comprises from 0.1% to 5% by weight and preferably from 0.1%to 3% by weight of microcapsules relative to the total weight of thesaid composition.

The obtained transparent gel with microcapsules present a pure and cleanappearance, with perfect stability under −20/20° C. (5 cycles), roomtemperature (25° C., 2 months), 37° C. (2 months) and 45° C. (2 months).The microcapsules release pigments during application without anyparticle feeling. Makeup results are perfectly and evenly provided afterapplication.

The transparent gel could also by slightly colored.

In this case, the transparent gel comprises at least one non-entrappedcolorant, in particular as disclosed here-after, preferably in an amountof less than 1 by weight based on the total weight of the totalcomposition.

Aqueous Phase

The microcapsules of the invention need to be in contact with an aqueousphase comprising water and at least one compound chosen from polyols,glycols, C₂-C₈ monoalcohols, and mixtures thereof in order to besoftened when applied on the keratinic material. This aqueous phase isparticularly advantageous for imparting and/or improving deformabilityto the microcapsules of the invention.

Advantageously this aqueous phase acts as a swelling agent or as asoftening agent towards the microcapsules without breaking them. Themicrocapsules are not inert when placed in this aqueous phase eitherthey swell: their diameter significantly increases with an optionalsoftening of the microcapsules, or the microcapsules significantlysoften without increasing of the diameter, they become more malleableand easier to break when applied onto the skin.

The aqueous phase used in the composition according to the invention isable to act on the softening kinetics of the microcapsules and moreparticularly it allows to obtain a good balance between softeningkinetics and hardness.

As a consequence, said aqueous phase is particularly advantageous forsoftening the microcapsules suitable for the present invention, in anappropriate way, since said aqueous phase plays a role on softeningkinetics of said microcapsules.

The aqueous phase comprises water and, where appropriate, awater-soluble solvent.

In the present invention, the term “water-soluble solvent” denotes acompound that is liquid at room temperature and water-miscible(miscibility with water of greater than 50% by weight at 25° C. andatmospheric pressure).

The water-soluble solvents that may be used in the composition of theinvention may also be volatile.

As said, the composition of the invention contains an aqueous phasecomprising water and at least one compound chosen among polyols,glycols, C₂-C₈ monoalcohols and mixtures thereof. It also may contain C₄ketones and C₂-C₄ aldehydes.

The composition of the invention contains microcapsules as defined aboveand an aqueous phase comprising water and at least one compound chosenfrom polyols, glycols, C₂-C₈ monoalcohols and mixtures thereof.Preferably the aqueous phase comprises water and the at least onecompound chosen from polyols, glycols and the mixtures thereof.

The aqueous phase is preferably present in an amount of at least 3% byweight, preferably at least 5% by weight, more preferably at least 8% byweight and advantageously at least 10% by weight relative to the weightof the composition.

Advantageously, the aqueous phase may be present in a content rangingfrom 30% to 99% by weight, preferably from 40% to 95% more preferablyfrom 50% to 90% by weight relative to the total weight of the saidcomposition.

Advantageously, water is present in an amount of at least 30% by weight,preferably at least 40% by weight, more preferably at least 50% byweight relative to the weight of the composition. Generally water ispresent in an amount ranging from 30% to 90% by weight, preferably 40%to 85% by weight and more preferably from 50 to 80% by weight, relativeto the weight of the composition.

Advantageously this aqueous phase acts as a swelling agent or as asoftening agent towards the microcapsules preferably without breakingthem or without triggering colorant leakage.

The composition of the invention will generally comprise at least onecompound chosen from polyols, glycols, C₂-C₈ monoalcohols, and mixturesthereof in amount ranging from 3% to 50% by weight, preferably from 5%to 45% by weight and more preferably from 10% to 45% by weight relativeto the total weight of the composition.

In a preferred embodiment, the aqueous phase suitable for the presentinvention comprises at least one C₂-C₈ monoalcohols.

In another preferred embodiment, the aqueous phase suitable for thepresent invention comprises at least one polyol or glycol.

In another preferred embodiment, the aqueous phase suitable for thepresent invention comprises at least one C₂-C₈ monoalcohols and at leastone polyol or glycol.

Monoalcohols or Lower Alcohols

Monoalcohol or lower alcohol that is suitable for use in the inventionmay be a compound of linear, branched or cyclic, saturated orunsaturated alkyl type, bearing only one —OH function.

Advantageously, C₂-C₈ monoalcohols are non cyclic monoalcohols, stillpreferably they are C₂-C₅ monoalcohols and preferably C₂-C₃monoalcohols.

The lower monoalcohols that are advantageously suitable for formulatinga composition according to the present invention are those especiallycontaining from 2 to 5 carbon atoms such as ethanol, propanol, butanol,isopropanol, isobutanol preferably ethanol and/or isopropanol and morepreferably at least ethanol.

A composition of the invention may comprise at least 1% by weight,preferably at least 2%, more preferably from 2% to 15%, advantageouslyfrom 3% to 10%, by weight and better still from 3% to 8% by weight,preferably from 4% to 6% by weight of mono-alcohol(s) relative to thetotal weight of said composition.

In a preferred embodiment, a composition of the invention comprisesethanol and/or isopropanol and more preferably at least ethanol, in atotal concentration of 2 to 15% by weight and more preferably of 3 to10% by weight relative to the total weight of said composition.

Lower monoalcohols such as ethanol can be advantageous used in many waysin the field of makeup and/or care of keratin material(s).

Such compounds are particularly useful for providing a fresh feeling tothe user when he applied on the skin, a composition of the invention.

Furthermore, such a feeling of freshness, pleasant as such to the user,may also advantageously allow to activate blood circulation in the skinwhere it is felt, especially in the skin surrounding the eyes whichforms a particularly well vascularized area. The fresh feelingaccompanying the application of these lower monoalcohols thus reducespuffiness and dark circles present in this part of the face due to thehigh vascularity and thinness in this part of the face.

The application of lower monoalcohols can also advantageously avoid theneed to apply other cooling agents such as menthol, ethyl menthanecarboxamide, menthyl lactate, menthoxypropanediol around the eyes, whichare generally raw material irritating to the eyes.

There is also a need to have at disposal compositions containingchanging color microcapsules in a physiological medium comprising alower alcohol because some cosmetic ingredients are particularly solublein hydroalcoholic media.

Furthermore, the lower monoalcohols such as ethanol allow to dissolveactive agents, especially keratolytic agents, such as, for example,salicylic acid and its derivatives.

Some microcapsules of the prior art rapidly disintegrate inhydroalcoholic media, as a consequence there was a need to have atdisposal compositions comprising changing color microcapsules stable inhydroalcoholic media.

Polyols and Glycols

For the purposes of the present invention, the term “polyol” should beunderstood as meaning any organic molecule comprising at least two freehydroxyl groups. The term “polyol” according to the invention does notencompass monosaccharide-alcohol disclosed above.

Preferably, a polyol in accordance with the present invention is presentin liquid form at room temperature.

The polyols/glycols are moisturizers or humectants.

They may have an effect towards the stability of other ingredients ofthe composition particularly towards microcapsules of the prior art.

There is thus a need to have at disposal stable compositions containingchanging color microcapsules in a physiological medium comprising apolyol and/or a glycol because these compositions present a noticeablemoisturizing or humecting effect.

This technical problem is solved by the compositions according to theinvention. A polyol that is suitable for use in the invention may be acompound of linear, branched or cyclic, saturated or unsaturated alkyltype, bearing on each alkyl chain at least two —OH functions, inparticular at least three —OH functions and more particularly at leastfour —OH functions.

The polyols that are advantageously suitable for formulating acomposition according to the present invention are those especiallycontaining from 2 to 32 carbon atoms preferably 2 to 20 carbon atoms andmore preferably 2 to 16 carbon atoms, advantageously 2 to 10 carbonatoms, more advantageously 2 to 6 carbon atoms.

According to another embodiment, a polyol that is suitable for use inthe invention may be advantageously chosen from polyethylene glycols.

According to one embodiment, a composition of the invention may comprisea mixture of polyols.

Advantageously, the polyol may be chosen from polyhydric alcohols,preferably of C₂-C₈ and more preferably C₃-C₆. The polyol may be chosenfrom glycerol, pentaerythritol, trimethylolpropane, ethylene glycol,propylene glycol, 1,3-butylene glycol, 1,3-propanediol, pentyleneglycol, hexylene glycol, isoprene glycol, dipropylene glycol, diethyleneglycol and diglycerol, ethylhexylglycerine, caprylyl glycol and mixturesthereof, glycerol and derivatives thereof, polyglycerols, such asglycerol oligomers, for instance diglycerol, and polyethylene glycols,glycol ethers (especially containing from 3 to 16 carbon atoms) such asmono-, di- or tripropylene glycol (C₁-C₄)alkyl ethers, mono-, di- ortriethylene glycol (C₁-C₄)alkyl ethers, and mixtures thereof.

Particularly, the polyol is selected from the group consisting inglycerol, glycols, preferably propylene glycol, butylene glycol,pentylene glycol, hexylene glycol, dipropylene glycol, diethyleneglycol, ethylhexylglycerine, caprylyl glycol, glycol ethers, preferablymono-, di- or tripropylene glycol of alkyl(C1-C4)ether or mono-, di- ortriethylene glycol of alkyl(C1-C4)ether, and mixtures thereof.

According to one preferred embodiment of the invention, the said polyolis chosen from ethylene glycol, pentaerythritol, trimethylolpropane,propylene glycol, butylene glycol, glycerol, polyglycerols andpolyethylene glycols, and mixtures thereof.

In a particular embodiment, the polyol is selected from the groupconsisting in glycerol, and glycols chosen from propylene glycol,butylene glycol, ethylhexylglycerine, caprylyl glycol and mixturesthereof.

According to one particular embodiment, the composition of the inventioncomprises at least butylene glycol, glycerol or a mixture thereof.

In a preferred embodiment, the composition comprises at least glycerol.

According to one particular embodiment, the composition of the inventioncomprises glycerol as sole polyol.

Advantageously the composition may comprise from 1 to 10, preferablyfrom 2 to 8 weight percent of glycerol based on the total weight of thecomposition.

Advantageously the composition may comprise from 1 to 10, preferablyfrom 2 to 8 weight percent of butylene glycol based on the total weightof the composition.

Advantageously the composition may comprise from 1 to 10, preferablyfrom 2 to 8 weight percent of propylene glycol based on the total weightof the composition.

When the composition comprises glycerol and at least one glycol, theweight ratio of glycerol/glycol is advantageously from 1/2 to 3/2,preferably from 2/3 to 1/1 more preferably around 1.

In a preferred embodiment, the composition comprises glycerol and atleast one glycol chosen from propylene glycol, butylene glycol,ethylhexylglycerine, caprylyl glycol, the weight ratio ofglycerol/glycol is advantageously from 1/2 to 3/2, preferably from 2/3to 1/1 more preferably around 1.

A composition according to the invention may advantageously comprise atleast 10% by weight, preferably between 10 and 45% by weight and inparticular between 10% and 40% by weight of polyol(s) and/or glycols,preferably one C₂-C₃₂ polyol and/or glycol, based on weight of thecomposition.

A composition according to the invention may advantageously comprise atleast 10% by weight, preferably from 12% to 50% by weight and inparticular from 13% to 40%, more preferably from 14 to 35% and betterfrom 15% to 30% by weight of polyol(s) and/or glycols based on weight ofthe composition.

A composition according to the invention may advantageously comprise atleast 10% by weight, preferably from 12% to 50% by weight and inparticular from 13% to 40%, more preferably from 14 to 35% and betterfrom 15% to 30% by weight of polyol(s) and/or glycols based on weight ofthe aqueous phase.

Preferably the polyol is a C₂-C₃₂ polyol and/or glycol.

Advantageously the weight ratio of polyol and glycol/composition is from1/10 to 1/2 preferably from 1/8 to 1/3, more preferably from 1/6 to 1/4.More particularly the weight ratio of polyol and glycol/aqueous phase isfrom 1/10 to 1/2 preferably from 1/8 to 1/3, more preferably from 1/6 to1/4.

Cosmetic Medium and Additional Ingredients

The gel composition according to the invention is cosmeticallyacceptable that is it contains a physiologically acceptable medium whichis non toxic and appropriate to be applied on the keratin material ofhuman beings.

“Cosmetically acceptable” in the sense of the present invention means acomposition with pleasant appearance, odor or feeling.

The “physiologically acceptable medium” is generally adapted to the formof under which the composition is intended to be conditioned.

Depending upon the form and the aim of the skin care or make-uppreparation, the composition of the invention will comprise, in additionto the microcapsules containing colorant, further additional cosmeticingredient(s) such as the ones selected from surfactants, fillers,thickening agents, film forming agents, polymers, preservatives,silicone elastomere, self-tanning agents, additional non-entrappedcolorants, actives, UV filters, perfumes, pH regulators and mixturesthereof.

The pH of the cosmetic composition according to the present inventionranges preferably from 6.5 to 7.5. A preferred base to modify the pH istriethanolamine.

It is a matter of routine operations for a person skilled in the art toadjust the nature and amount of the additives present in thecompositions in accordance with the invention such that the desiredcosmetic properties thereof are not thereby affected. Some of theseconventional ingredients are detailed here-after.

Tanning Agents

For the purposes of the present invention, the expression “skinself-tanning agent” means a compound that is capable of producing, oncontact with the skin, a coloured reaction with the free amine functionspresent in the skin, such as amino acids, peptides or proteins.

Other characteristics, aspects and advantages of the present inventionwill emerge on reading the detailed description that follows.

The self-tanning agents are generally chosen from certain monocarbonylor polycarbonyl compounds, for instance isatin, alloxan, ninhydrin,glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose,pyrazoline-4,5-dione derivatives as described in patent application FR 2466 492 and WO 97/35842, dihydroxyacetone (DHA), and4,4-dihydroxypyrazolin-5-ones as described in patent application EP 903342. DHA will preferably be used.

DHA may be used in free and/or encapsulated form, for example in lipidvesicles such as liposomes, especially described in patent applicationWO 97/25970.

The self-tanning agent(s) is (are) generally present in proportionsranging from 0.1% to 15% by weight, preferably from 0.2% to 10% byweight and more preferentially from 1% to 8% by weight relative to thetotal weight of the composition.

Silicone Elastomers

According to the present invention, compositions may comprise at leastone silicone elastomer. Any suitable silicone elastomer can be used inaccordance with the present invention. Suitable silicone elastomersinclude, for example, emulsifying silicone elastomers such aspolyglycerolated and/or hydrophilic emulsifying silicone elastomers suchas alkoxylated silicone elastomers, and non-emulsifying siliconeelastomers. Such silicone elastomers can be spherical or non-spherical.

Polyglycerolated Silicone Elastomers

Suitable polyglycerolated silicone elastomers include, for example,crosslinked elastomeric organopolysiloxanes that may be obtained by acrosslinking addition reaction of diorganopolysiloxane containing atleast one hydrogen atom linked to silicon and of polyglycerolatedcompounds containing ethylenically unsaturated groups, especially in thepresence of a platinum catalyst.

Polyglycerolated silicone elastomers that may be used include, but arenot limited to, those sold under the names “KSG-710”, “KSG-810”,“KSG-820”, “KSG-830” and “KSG-840” by the company Shin-Etsu. Suitablepolygycerolated silicone elastomers are also disclosed in U.S. Ser. No.11/085,509, filed Mar. 22, 2005 (published as U.S. patent applicationpublication no. 2005/0220728), the entire disclosure of which is herebyincorporated by reference.

Hydrophilic Emulsifying Silicone Elastomers

The term “hydrophilic emulsifying silicone elastomer” means a siliconeelastomer comprising at least one hydrophilic chain other than apolyglycerolated chain as described above.

In particular, the hydrophilic emulsifying silicone elastomer may bechosen from polyoxyalkylenated silicone elastomers.

Suitable polyoxyalkylenated elastomers are described in U.S. Pat. No.5,236,986, U.S. Pat. No. 5,412,004, U.S. Pat. No. 5,837,793 and U.S.Pat. No. 5,811,487.

Suitable polyoxyalkylenated silicone elastomers that may be used includethose sold under the names “KSG-21”, “KSG-20”, “KSG-30”, “KSG-31”,“KSG-32”, “KSG-33”, “KSG-210”, “KSG-310”, “KSG-320”, “KSG-330”,“KSG-340” and “X-226146” by the company Shin-Etsu, or “DC9010” and“DC9011” by the company Dow Corning.

Suitable hydrophilic emulsifying silicone elastomers are also disclosedin U.S. Ser. No. 11/085,509, filed Mar. 22, 2005 (published as U.S.patent application publication no. 2005/0220728).

Non-Emulsifying Silicone Elastomers

The term “non-emulsifying” defines elastomers not containing ahydrophilic chain, such as polyoxyalkylene or polyglycerolated units.

The non-emulsifying silicone elastomer is preferably an elastomericcrosslinked organopolysiloxane that may be obtained by a crosslinkingaddition reaction of diorganopolysiloxane containing at least onehydrogen linked to silicon and of diorganopolysiloxane containingethylenically unsaturated groups linked to silicon, especially in thepresence of a platinum catalyst; or by dehydrogenation crosslinkingcoupling reaction between a diorganopolysiloxane containing hydroxyl endgroups and a diorganopolysiloxane containing at least one hydrogenlinked to silicon, especially in the presence of an organotin compound;or by a crosslinking coupling reaction of a diorganopolysiloxanecontaining hydroxyl end groups and of a hydrolysable organopolysilane;or by thermal crosslinking of organopolysiloxane, especially in thepresence of an organoperoxide catalyst; or by crosslinking oforganopolysiloxane via high-energy radiation such as gamma rays,ultraviolet rays or an electron beam.

Suitable non-emulsifying silicone elastomers are described in patentapplications JP61-194009 A, EP0242219 A, EP0295886 A and EP0765656 A.

Suitable non-emulsifying silicone elastomers that may be used include,but are not limited to, those sold under the names “DC 9040”, “DC 9041”,“DC 9509”, “DC 9505” and “DC 9506” by the company Dow Corning.

Suitable non-emulsifying silicone elastomers are also disclosed in U.S.Ser. No. 11/085,509, filed Mar. 22, 2005 (published as U.S. patentapplication publication no. 2005/0220728).

The non-emulsifying silicone elastomer may also be in the form ofelastomeric crosslinked organopolysiloxane powder coated with siliconeresin, especially with silsesquioxane resin, as described, for example,in U.S. Pat. No. 5,538,793, the entire content of which is hereinincorporated by reference. Such elastomers are sold under the names“KSP-100”, “KSP-101”, “KSP-102”, “KSP-103”, “KSP-104” and “KSP-105” bythe company Shin-Etsu.

Other elastomeric crosslinked organopolysiloxanes in the form of powdersinclude hybrid silicone powders functionalized with fluoroalkyl groups,sold especially under the name “KSP-200” by the company Shin-Etsu;hybrid silicone powders functionalized with phenyl groups, soldespecially under the name “KSP-300” by the company Shin-Etsu.

The silicone elastomer may be present in the compositions of the presentinvention in an amount of from 0.1% to 95% by weight, preferably from0.1% to 75% by weight, more preferably from 0.1 to 50% by weight, morepreferably from 0.1% to 40% by weight, more preferably from 0.5% to 30%by weight, more preferably from 0.5% to 25% by weight, more preferablyfrom 1% to 20%, more preferably from 1% to 15% and even more preferablyfrom 3% to 10% by weight based on the weight of the composition.

Film-Forming Agents

Silicone Polyamide

The compositions according to the invention comprise at least onesilicone polyamide.

The silicone polyamides of the composition are preferably solid at roomtemperature (25° C.) and atmospheric pressure (760 mmHg).

The silicone polyamides of the composition of the invention may bepolymers of the polyorganosiloxane type, for instance those described indocuments U.S. Pat. No. 5,874,069, U.S. Pat. No. 5,919,441, U.S. Pat.No. 6,051,216 and U.S. Pat. No. 5,981,680. According to the invention,the silicone polymers may belong to the following two families:

(1) polyorganosiloxanes comprising at least two amide groups, these twogroups being located in the polymer chain, and/or

(2) polyorganosiloxanes comprising at least two amide groups, these twogroups being located on grafts or branches.

A) According to a first variant, the silicone polymers arepolyorganosiloxanes as defined above in which the amide units arelocated in the polymer chain.

The silicone polyamides may be more particularly polymers comprising atleast one unit corresponding to the general formula I:

-   -   1) in which: G′ represents C(O) when G represents        —C(O)—NH—Y—NH—, and G′ represents —NH— when G represents        —NH—C(O)—Y—C(O)—,    -   2) R⁴, R⁵, R⁶ and R⁷, which may be identical or different,        represent a group chosen from:        -   linear, branched or cyclic, saturated or unsaturated, C₁ to            C₄₀ hydrocarbon-based groups, possibly containing in their            chain one or more oxygen, sulfur and/or nitrogen atoms, and            possibly being partially or totally substituted with            fluorine atoms,        -   C₆-C₁₀ aryl groups, optionally substituted with one or more            C₁-C₄ alkyl groups,        -   polyorganosiloxane chains possibly containing one or more            oxygen, sulfur and/or nitrogen atoms,    -   3) the groups X, which may be identical or different, represent        a linear or branched C₁ to C₃₀ alkylenediyl group, possibly        containing in its chain one or more oxygen and/or nitrogen        atoms;    -   4) Y is a saturated or unsaturated C₁ to C₅₀ linear or branched        alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene        divalent group, which may comprise one or more oxygen, sulfur        and/or nitrogen atoms, and/or may bear as substituent one of the        following atoms or groups of atoms: fluorine, hydroxyl, C₃ to C₈        cycloalkyl, C₁ to C₄₀ alkyl, C₅ to C₁₀ aryl, phenyl optionally        substituted with one to three C₁ to C₃ alkyl, C₁ to C₃        hydroxyalkyl and C₁ to C₆ aminoalkyl groups, or    -   5) Y represents a group corresponding to the formula:

-   -   -   in which:            -   T represents a linear or branched, saturated or                unsaturated, C₃ to C₂₄ trivalent or tetravalent                hydrocarbon-based group optionally substituted with a                polyorganosiloxane chain, and possibly containing one or                more atoms chosen from O, N and S, or T represents a                trivalent atom chosen from N, P and Al, and            -   R⁸ represents a linear or branched C₁-C₅₀ alkyl group or                a polyorganosiloxane chain, possibly comprising one or                more ester, amide, urethane, thiocarbamate, urea,                thiourea and/or sulfonamide groups, which may possibly                be linked to another chain of the polymer;

    -   6) n is an integer ranging from 2 to 500 and preferably from 2        to 200, and m is an integer ranging from 1 to 1000, preferably        from 1 to 700 and better still from 6 to 200.

According to the invention, 80% of the groups R⁴, R⁵, R⁶ and R⁷ of thepolymer are preferably chosen from methyl, ethyl, phenyl and3,3,3-trifluoropropyl groups. According to another embodiment, 80% ofthe groups R⁴, R⁵, R⁶ and R⁷ of the polymer are methyl groups.

According to the invention, Y can represent various divalent groups,furthermore optionally comprising one or two free valencies to establishbonds with other moieties of the polymer or copolymer. Preferably, Yrepresents a group chosen from:

-   -   a) linear C₁ to C₂₀ and preferably C₁ to C₁₀ alkylene groups,    -   b) branched C₃₀ to C₅₆ alkylene groups possibly comprising rings        and unconjugated unsaturations,    -   c) C₅-C₆ cycloalkylene groups,    -   d) phenylene groups optionally substituted with one or more C₁        to C₄₀ alkyl groups,    -   e) C₁ to C₂₀ alkylene groups comprising from 1 to 5 amide        groups,    -   f) C₁ to C₂₀ alkylene groups comprising one or more substituents        chosen from hydroxyl, C₃ to C₈ cycloalkane, C₁ to C₃        hydroxyalkyl and C₁ to C₆ alkylamine groups,    -   g) polyorganosiloxane chains of formula:

-   -   -   in which R⁴, R⁵, R⁶, R⁷, T and m are as defined above.        -   B) According to the second variant, the silicone polyamides            may be polymers comprising at least one unit corresponding            to formula (II):

-   -   -   in which:            -   R⁴ and R⁶, which may be identical or different, are as                defined above for formula (I),            -   R¹⁰ represents a group as defined above for R⁴ and R⁶,                or represents a group of formula —X-G″—R¹² in which X is                as defined above for formula (I) and R¹² represents a                hydrogen atom or a linear, branched or cyclic, saturated                or unsaturated, C₁-C₅₀ hydrocarbon-based group                optionally comprising in its chain one or more atoms                chosen from O, S and N, optionally substituted with one                or more fluorine atoms and/or one or more hydroxyl                groups, or a phenyl group optionally substituted with                one or more C₁-C₄ alkyl groups,        -   and G″ represents —C(O)NH— and —HN—C(O)—,            -   R¹¹ represents a group of formula —X-G″—R¹² in which X,                G″ and R¹² are as defined above,            -   m₁ is an integer ranging from 1 to 998, and            -   m₂ is an integer ranging from 2 to 500.

According to the invention, the silicone polymer may be a homopolymer,i.e. a polymer comprising several identical units, in particular unitsof formula (I) or of formula (II).

According to the invention, it is also possible to use a siliconepolymer formed from a copolymer comprising several different units offormula (I), i.e. a polymer in which at least one of the groups R⁴, R⁵,R⁶, R⁷, X, G, Y, m and n is different in one of the units. The copolymermay also be formed from several units of formula (II), in which at leastone of the groups R⁴, R⁶, R¹⁰, R¹¹, m₁ and m₂ is different in at leastone of the units.

It is also possible to use a polymer comprising at least one unit offormula (I) and at least one unit of formula (II), the units of formula(I) and the units of formula (II) possibly being identical to ordifferent from each other.

These copolymers may be block polymers or grafted polymers.

In this first embodiment of the invention, the silicone polymer may alsoconsist of a grafted copolymer. Thus, the polyamide containing siliconeunits may be grafted and optionally crosslinked with silicone chainscontaining amide groups. Such polymers may be synthesized withtrifunctional amines.

According to one advantageous embodiment of the invention, the groupscapable of establishing hydrogen interactions are amide groups offormulae —C(O)NH— and —HN—C(O)—. In this case, the structuring agent maybe a polymer comprising at least one unit of formula (III) or (IV):

in which R⁴, R⁵, R⁶, R⁷, X, Y, m and n are as defined above.

In these polyamides of formula (III) or (IV), m is in the range from 1to 700, in particular from 15 to 500 and especially from 50 to 200, andn is in particular in the range from 1 to 500, preferably from 1 to 100and better still from 4 to 25,

-   -   X is preferably a linear or branched alkylene chain containing        from 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms,        especially from 5 to 15 carbon atoms and more particularly 10        carbon atoms, and    -   Y is preferably an alkylene chain that is linear or branched or        that possibly comprises rings and/or unsaturations, containing        from 1 to 40 carbon atoms, in particular from 1 to 20 carbon        atoms and better still from 2 to 6 carbon atoms, in particular 6        carbon atoms.

In formulae (III) and (IV), the alkylene group representing X or Y canoptionally contain in its alkylene portion at least one of the followingmembers:

-   -   1) 1 to 5 amide, urea, urethane or carbamate groups,    -   2) a C₅ or C₆ cycloalkyl group, and    -   3) a phenylene group optionally substituted with 1 to 3        identical or different C₁ to C₃ alkyl groups.

In formulae (III) and (IV), the alkylene groups may also be substitutedwith at least one member chosen from the group consisting of:

-   -   a hydroxyl group,    -   a C₃ to C₈ cycloalkyl group,    -   one to three C₁ to C₄₀ alkyl groups,    -   a phenyl group optionally substituted with one to three C₁ to C₃        alkyl groups,    -   a C₁ to C₃ hydroxyalkyl group, and    -   a C₁ to C₆ aminoalkyl group.

In these formulae (III) and (IV), Y may also represent:

in which R⁸ represents a polyorganosiloxane chain and T represents agroup of formula:

in which a, b and c are, independently, integers ranging from 1 to 10,and R¹³ is a hydrogen atom or a group such as those defined for R⁴, R⁵,R⁶ and R⁷.

In formulae (III) and (IV), R⁴, R⁵, R⁶ and R⁷ preferably represent,independently, a linear or branched C₁ to C₄₀ alkyl group, preferably aCH₃, C₂H₅, n-C₃H₇ or isopropyl group, a polyorganosiloxane chain or aphenyl group optionally substituted with one to three methyl or ethylgroups.

As has been seen previously, the polymer may comprise identical ordifferent units of formula (III) or (IV).

Thus, the polymer may be a polyamide containing several units of formula(III) or (IV) of different lengths, i.e. a polyamide corresponding toformula (V):

in which X, Y, n and R⁴ to R⁷ have the meanings given above, m₁ and m₂,which are different, are chosen in the range from 1 to 1000, and p is aninteger ranging from 2 to 300.

In this formula, the units may be structured to form either a blockcopolymer, or a random copolymer or an alternating copolymer. In thiscopolymer, the units may be not only of different lengths, but also ofdifferent chemical structures, for example containing different groupsY. In this case, the polymer may correspond to formula VI:

in which R⁴ to R⁷, X, Y, m₁, m₂, n and p have the meanings given aboveand Y¹ is different from Y but chosen from the groups defined for Y. Aspreviously, the various units may be structured to form either a blockcopolymer, or a random copolymer or an alternating copolymer.

In this first embodiment of the invention, the structuring agent mayalso consist of a grafted copolymer. Thus, the polyamide containingsilicone units may be grafted and optionally crosslinked with siliconechains containing amide groups. Such polymers may be synthesized withtrifunctional amines.

In this case, the polymer may comprise at least one unit of formula(VII):

in which X¹ and X², which are identical or different, have the meaninggiven for X in formula (I), n is as defined in formula (I), Y and T areas defined in formula (I), R¹⁴ to R²¹ are groups chosen from the samegroup as R⁴ to R⁷, m₁ and m₂ are numbers in the range from 1 to 1000,and p is an integer ranging from 2 to 500.

In formula (VII), it is preferred that:

-   -   p is in the range from 1 to 25 and better still from 1 to 7,    -   R¹⁴ to R²¹ are methyl groups,    -   T corresponds to one of the following formulae:

in which R²² is a hydrogen atom or a group chosen from the groupsdefined for R⁴ to R⁷, and R²³, R²⁴ and R²⁵ are, independently, linear orbranched alkylene groups, and more preferably correspond to the formula:

in particular with R²³, R²⁴ and R²⁵ representing —CH₂—CH₂—,

-   -   m₁ and m₂ are in the range from 15 to 500 and better still from        15 to 45,    -   X¹ and X² represent —(CH₂)₁₀—, and    -   Y represents —CH₂—.

These polyamides containing a grafted silicone unit of formula (VII) maybe copolymerized with polyamide-silicones of formula (II) to form blockcopolymers, alternating copolymers or random copolymers. The weightpercentage of grafted silicone units (VII) in the copolymer may rangefrom 0.5% to 30% by weight.

According to the invention, as has been seen previously, the siloxaneunits may be in the main chain or backbone of the polymer, but they mayalso be present in grafted or pendent chains. In the main chain, thesiloxane units may be in the form of segments as described above. In thependent or grafted chains, the siloxane units may appear individually orin segments.

According to one embodiment variant of the invention, a copolymer ofsilicone polyamide and of hydrocarbon-based polyamide, or a copolymercomprising units of formula (III) or (IV) and hydrocarbon-basedpolyamide units, may be used. In this case, the polyamide-silicone unitsmay be located at the ends of the hydrocarbon-based polyamide.

According to one preferred embodiment, the silicone polyamide comprisesunits of formula III, preferably in which the groups R4, R5, R6 and R7represent methyl groups, one from among X and Y represents an alkylenegroup of 6 carbon atoms and the other represents an alkylene group of 11carbon atoms, n representing the degree of polymerization DP of thepolymer.

Examples of such silicone polyamides that may be mentioned include thecompounds sold by the company Dow Corning under the name DC2-8179 (DP100) and DC2-8178 (DP 15), the INCI name of which isNylon-611/dimethicone copolymers.

Advantageously, the silicone polyamides are compounds having the INCIname Nylon-611/dimethicone copolymers.

Advantageously, the composition according to the invention comprises atleast one polydimethylsiloxane block polymer of general formula (I) withan index m of about 100. The index “m” corresponds to the degree ofpolymerization of the silicone part of the polymer.

More preferably, the composition according to the invention comprises atleast one polymer comprising at least one unit of formula (III) in whichm ranges from 50 to 200, in particular from 75 to 150 and is moreparticularly about 100.

Preferably also, R⁴, R⁵, R⁶ and R⁷ independently represent, in formula(III), a linear or branched C₁-C₄₀ alkyl group, preferably a CH₃, C₂H₅,n-C₃H₇ or isopropyl group.

As examples of polymers that may be used, mention may be made of one ofthe silicone polyamides obtained in accordance with Examples 1 to 3 ofdocument U.S. Pat. No. 5,981,680.

Preferably, the nylon-611/dimethicone copolymer sold under the referenceDC2-8179 by Dow Corning is used as silicone polyamide.

The silicone polyamide may be present in the composition in a totalcontent ranging from 0.5% to 45% by weight relative to the total weightof the composition, preferably ranging from 1% to 30% by weight andbetter still ranging from 2% to 20% by weight relative to the totalweight of said composition.

Silicone Resin

Examples of these silicone resins that may be mentioned include:

-   -   siloxysilicates, which may be trimethylsiloxysilicates of        formula [(CH₃)₃SiO]_(x)(SiO_(4/2))_(y) (units MQ) in which x and        y are integers ranging from 50 to 80,    -   polysilsesquioxanes of formula (CH₃SiO_(3/2))_(x) (units T) in        which x is greater than 100 and at least one of the methyl        radicals of which may be substituted with a group R as defined        above,    -   polymethylsilsesquioxanes, which are polysilsesquioxanes in        which none of the methyl radicals is substituted with another        group. Such polymethylsilsesquioxanes are described in document        U.S. Pat. No. 5,246,694.

As examples of commercially available polymethylsilsesquioxane resins,mention may be made of those sold:

-   -   by the company Wacker under the reference Resin MK, such as        Belsil PMS MK: polymer comprising CH₃SiO_(3/2) repeating units        (units T), which may also comprise up to 1% by weight of        (CH₃)₂SiO_(2/2) units (units D) and having an average molecular        weight of about 10 000 g/mol, or    -   by the company Shin-Etsu under the reference KR-220L, which are        composed of units T of formula CH₃SiO_(3/2) and contain Si—OH        (silanol) end groups, under the reference KR-242A, which        comprise 98% of units T and 2% of dimethyl units D and contain        Si—OH end groups, or under the reference KR-251, comprising 88%        of units T and 12% of dimethyl units D and contain Si—OH end        groups.

Siloxysilicate resins that may be mentioned include trimethylsiloxysilicate resins (TMS) optionally in the form of powders. Suchresins are sold under the reference SR1000 by the company MomentivePerformance Materials or under the reference TMS 803 by the companyWacker. Mention may also be made of trimethyl siloxysilicate resins soldin a solvent such as cyclomethicone, sold under the name KF-7312J by thecompany Shin-Etsu or DC 749 and DC 593 by the company Dow Corning.

Advantageously, the silicone resin, for instance the trimethylsiloxysilicate resin, is present in a content ranging from 0.5% to 30%,or better still from 1% to 25% or even better still from 5% to 25%relative to the total weight of the composition.

Preferably, nylon-611/dimethicone is used as silicone polyamide and atrimethyl siloxysilicate resin is used as silicone resin.

According to another embodiment, the silicone resins are,propylphenylsilsesquioxane resins.

Silsesquioxane resins are a specific form of film forming siliconeresins. Silicone resins are crosslinked organopolysiloxanes which aresolid at room temperature and generally soluble in organic solvents.When they are soluble in volatile solvents, silicone resins are capableof forming a film once the solvent has evaporated. Furthermore, if thesolvent dissolving the silicone resin is absorbed on the substrate ontowhich it is applied, the silicone resin which remains on the substratemay also form a film.

The compositions of the present invention comprisepropylphenylsilsesquioxane resins, which have been disclosed in patentpublications WO2005/090444, published on Sep. 29, 2005; US20040180011,published on Sep. 16, 2004; and US20040156806, published on Aug. 12,2004.

The propylphenylsilsesquioxane resin comprises at least about 70 mole %of propyl siloxy units (C₃H₇SiO_(3/2)), based on the total mole % siloxyunits of the resin, and at most about 30 mole % of phenyl siloxy units(C₆H₅SiO_(3/2)), based on the total mole siloxy units of the resin.

The mole % of propyl siloxy units to phenyl siloxy units can be adjusteddepending on an intended application. As such, it is possible to havepropylphenylsilsesquioxane resins having a mole % propyl siloxyunits:phenyl siloxy units ranging from about 70:30 to about 100:0, suchas 70:30; 80:20; 90:10; and 100:0; and subranges therebetween. When themole % of the propyl siloxy units is about 100 mole %, thepropylphenylsilsesquioxane resin is referred to as apropylsilsesquioxane resin.

A suitable example of a propylphenylsilsesquioxane resin for use incosmetic compositions of the present invention includes, but is notlimited to, a propylsilsesquioxane resin commercially available fromDow-Corning under the tradename DC 670 Fluid.

The propylphenylsilsesquioxane film forming resin may be present in anamount ranging from about 0.5% to about 50% by weight, such as fromabout 1% to about 40% by weight, such as from about 2% to about 30% byweight, such as from about 3% to about 20% by weight, and such as fromabout 4% to about 10% by weight, all weights based on the weight of thecomposition as a whole.

Silicone Acrylate Copolymers

The gel composition of the present invention may contain siliconeacrylate copolymers.

Silicone acrylate copolymers are another specific form of film formingsilicone resins. They are available as silicone acrylate copolymers witha (meth)acrylate backbone grafted with a silicone chain or as a siliconebackbone grafted with a (meth)acrylate, or as a silicone acrylatedendrimer.

Silicone acrylate dendrimers, such as those described and claimed inU.S. Pat. No. 6,280,748, the entire contents of which is herebyincorporated by reference, are preferred for use in the composition ofthe present invention. The silicone acrylate dendrimer is comprised of avinyl polymer having a carbosiloxane dendrimer structure in its sidemolecular chain. It is characterized by a vinyl-type polymer which hasin its side molecular chain a carbosiloxane dendrimer structure. Theterm “carbosiloxane dendrimer structure” is a structure withhigh-molecular-weight groups branched with high regularity in a radialdirection from a single core.

The vinyl polymer backbone is formed from a vinyl-type monomer whichcontains a radical polymerizable vinyl group. In its broadestdefinition, there are no particular limitations with regards to the typeof such a monomer. A particularly preferred vinyl polymer is a(meth)acrylate.

The number-average molecular weight of the silicone acrylate dendrimersfor use in the composition of the present invention ranges from about3,000 to about 2,000,000, such as from about 5,000 to about 800,000.

Particularly preferred silicone acrylate dendrimers for use in thecomposition of the present invention are available from Dow Corning asFA-4001 CM silicone acrylate, a 30% solution in cyclomethicone, and asFA-4002 ID silicone acrylate, a 40% solution in isododecane, under theINCI name of Acrylates/Polytrimethylsiloxymethacrylate Copolymer.

The silicone acrylate copolymer may be present in the composition of theinvention in an amount ranging from about 0.5% to about 20% by weight,such as from about 0.7% to about 15% by weight, such as from about 1% toabout 10% by weight, all weights based on the weight of the compositionas a whole.

Pulverulent Phase

A composition of the invention may contain a pulverulent phase materialsbesides the microcapsules defined above.

A composition according to the invention may comprise at least 1% byweight and more particularly at least 5% by weight of pulverulent phaserelative to the total weight of the said composition.

More particularly, a composition according to the invention may compriseat least 15% by weight and more particularly at least 20% by weight ofpulverulent phase relative to the total weight of the said composition.

For the purposes of the present invention, this pulverulent phase maycomprise, besides the microcapsules required according to the invention,at least one non-entrapped particulate material chosen from fillers;pigments; nacres; particles with a metallic tint; and mixtures thereof.

Thus, a composition according to the invention advantageously maycomprise from 1% to 70% by weight, preferably from 5% to 60% by weightand better still from 10% to 50% by weight of pulverulent phase relativeto the total weight of the said composition.

Thus, a composition according to the invention advantageously maycomprise from 15% to 70% by weight, preferably from 20% to 60% by weightand better still from 25% to 50% by weight of pulverulent phase relativeto the total weight of the said composition.

a) Non Entrapped Filler

For the purposes of the present invention, the term “fillers” should beunderstood as meaning colourless or white solid particles of any form,which are in an insoluble and dispersed form in the medium of thecomposition.

These fillers, of mineral or organic, natural or synthetic nature, givethe composition containing them softness and give the makeup result amatt effect and uniformity.

A composition according to the invention may comprise from 0.5% to 50%by weight and preferably from 1% to 30% by weight of fillers relative tothe total weight of the said composition.

This amount of fillers does not include the amount of hollow particlesrequired in parallel according to the invention.

Among the mineral fillers that may be used in the compositions accordingto the invention, mention may be made of natural or synthetic mica,talc, kaolin, natural or synthetic sericite, silica, hydroxyapatite,boron nitride, calcium carbonate, hollow silica microspheres (Silicabeads from Maprecos), glass or ceramic microcapsules; composites ofsilica and titanium dioxide, such as the TSG series sold by Nippon SheetGlass, and mixtures thereof.

Among the organic fillers that may be used in the compositions accordingto the invention, mention may be made of polyamide powders (Nylon®Orgasol from Atochem), poly-β-alanine powder and polyethylene powder,polytetrafluoroethylene (Teflon®) powder, lauroyllysine,tetrafluoroethylene polymer powders, spherical powders of crosslinkedelastomeric organopolysiloxane, described especially in documentJP-A-02-243612, such as those sold under the name Trefil Powder E 2-506Cor DC9506 or DC9701 by the company Dow Corning, silicone resins, whichare products of hydrolysis and polycondensation of siloxane mixtures offormulae (R)3SiOHCH3 and Si(OCH3)4, R representing an alkyl groupcontaining from 1 to 6 carbon atoms (for example KSP100 from Shin-Etsu),silicone resin microbeads (for example Tospearl® from Toshiba),Polypore® L200 (Chemdal Corporation), polyurethane powders, inparticular crosslinked polyurethane powders comprising a copolymer, thesaid copolymer comprising trimethylol hexyl lactone, for instance thepolymer of hexamethylene diisocyanate/trimethylol hexyl lactone, soldunder the name Plastic powder D-400® or Plastic Powder D-800® by thecompany Toshiki, and mixtures thereof.

Among the other organic fillers that may be used in the compositionsaccording to the invention, mention may be made of starch-based orcellulose-based powders. Examples of such fillers that may be mentionedinclude the Dry Flo products sold by Akzo Nobel and the Cellubeadsproducts sold by the company Daito Kasei.

Advantageously, the fillers in accordance with the invention are mineralfillers, preferably chosen from mica, sericite, kaolin, talc and silica,and mixtures thereof.

c) Non Entrapped Particulate Materials for Colouring Purposes.

These additional colouring particulate materials may be present in aproportion of from 0 to 40% by weight, preferably from 1% to 30% byweight or even 5% to 30% by weight relative to the total weight of thecomposition containing them.

They may especially be pigments, nacres and/or particles with metallictint products, these materials possibly being surface-treated.

The term “pigments” should be understood as meaning white or coloured,mineral or organic particles that are insoluble in an aqueous solution,which are intended to colour and/or opacify the composition containingthem.

A composition according to the invention may comprise from 0.01% to 40%by weight, preferably from 0.1% to 20% by weight and better still from1% to 15% by weight of pigments relative to the total weight of saidcomposition.

The pigments may be white or coloured, and mineral and/or organic.

As mineral pigments that may be used in the invention, mention may bemade of titanium oxide, titanium dioxide, zirconium oxide, zirconiumdioxide, cerium oxide or cerium dioxide and also zinc oxide, iron oxideor chromium oxide, ferric blue, manganese violet, ultramarine blue andchromium hydrate, and mixtures thereof.

According to a specific embodiment, the composition of the inventioncontain at least non-entrapped inorganic pigments chosen from titaniumdioxide, zinc oxide, cerium oxide, and/or fillers chosen from bismuthoxychloride or boron nitride, in order to improve the white color of thecomposition.

According to a specific embodiment, the compositions of the inventioncontain at least non-entrapped TiO₂.

It may also be a pigment having a structure that may be, for example, ofsericite/brown iron oxide/titanium dioxide/silica type. Such a pigmentis sold, for example, under the reference Coverleaf NS or JS by thecompany Chemicals and Catalysts, and has a contrast ratio in the regionof 30.

They may also be pigments having a structure that may be, for example,of silica microsphere type containing iron oxide. An example of apigment having this structure is the product sold by the company Miyoshiunder the reference PC Ball PC-LL-100 P, this pigment being constitutedof silica microspheres containing yellow iron oxide.

Advantageously, the pigments in accordance with the invention are ironoxides and/or titanium dioxides.

The term “nacres” should be understood as meaning iridescent ornon-iridescent coloured particles of any shape, especially produced bycertain molluscs in their shell or alternatively synthesized, which havea colour effect via optical interference.

A composition of the invention may comprise from 1% to 80% by weight,preferably from 5% to 60% by weight and better still from 10% to 40% byweight of nacres relative to the total weight of said composition.

The nacres may be chosen from nacreous pigments such as titanium micacoated with an iron oxide, titanium mica coated with bismuthoxychloride, titanium mica coated with chromium oxide, titanium micacoated with an organic dye and also nacreous pigments based on bismuthoxychloride. They may also be mica particles at the surface of which aresuperposed at least two successive layers of metal oxides and/or oforganic dyestuffs.

Examples of nacres that may also be mentioned include natural micacoated with titanium oxide, with iron oxide, with natural pigment orwith bismuth oxychloride.

Among the nacres available on the market, mention may be made of thenacres Timica, Flamenco and Duochrome (based on mica) sold by thecompany Engelhard, the Timiron nacres sold by the company Merck, thePrestige mica-based nacres, sold by the company Eckart, and the Sunshinesynthetic mica-based nacres, sold by the company Sun Chemical.

The nacres may more particularly have a yellow, pink, red, bronze,orange, brown, gold and/or coppery colour or tint.

As illustrations of nacres that may be used in the context of thepresent invention, mention may be made of gold-coloured nacres soldespecially by the company Engelhard under the name Brilliant gold 212G(Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504(Chromalite) and Monarch gold 233× (Cloisonne); the bronze nacres soldespecially by the company Merck under the names Bronze fine (17384)(Colorona) and Bronze (17353) (Colorona) and by the company Engelhardunder the name Super bronze (Cloisonne); the orange nacres soldespecially by the company Engelhard under the names Orange 363C(Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck underthe names Passion orange (Colorona) and Matte orange (17449) (Microna);the brown-tinted nacres sold especially by the company Engelhard underthe names Nuantique copper 340XB (Cloisonne) and Brown CL4509(Chromalite); the nacres with a copper tint sold especially by thecompany Engelhard under the name Copper 340A (Timica); the nacres with ared tint sold especially by the company Merck under the name Sienna fine(17386) (Colorona); the nacres with a yellow tint sold especially by thecompany Engelhard under the name Yellow (4502) (Chromalite); thered-tinted nacres with a golden tint sold especially by the companyEngelhard under the name Sunstone G012 (Gemtone); the pink nacres soldespecially by the company Engelhard under the name Tan opale G005(Gemtone); the black nacres with a golden tint sold especially by thecompany Engelhard under the name Nu antique bronze 240 AB (Timica); theblue nacres sold especially by the company Merck under the name Matteblue (17433) (Microna); the white nacres with a silvery tint soldespecially by the company Merck under the name Xirona Silver; and thegolden-green pinkish-orange nacres sold especially by the company Merckunder the name Indian summer (Xirona), and mixtures thereof.

Advantageously, the nacres in accordance with the invention are micascoated with titanium dioxide or with iron oxide, and also bismuthoxychloride.

The term “particles with a metallic tint”, within the meaning of thepresent invention, denotes particles whose nature, size, structure andsurface state allow them to reflect the incident light, especially in anon-iridescent manner.

A composition according to the invention may comprise from 1% to 50% byweight and preferably from 1% to 20% by weight of particles with ametallic tint relative to the total weight of said composition.

Particles with a substantially flat outer surface are also suitable,since they can, if their size, structure and surface state allow it,more easily give rise to a strong specular reflection, which may then betermed a mirror effect.

The particles with a metallic tint that may be used in the inventionmay, for example, reflect light in all the components of the visibleregion without significantly absorbing one or more wavelengths. Thespectral reflectance of these particles may, for example, be greaterthan 70% and better still at least 80%, or even 90% or 95%, in the range400-700 nm.

These particles generally have a thickness of less than or equal to 1μm, especially less than or equal to 0.7 μm and in particular less thanor equal to 0.5 μm.

The particles with a metallic tint that may be used in the invention arein particular chosen from:

-   -   particles of at least one metal and/or of at least one metal        derivative,    -   particles comprising a monomaterial or multimaterial organic or        mineral substrate, at least partially coated with at least one        layer with a metallic tint comprising at least one metal and/or        at least one metal derivative, and

mixtures of said particles.

Among the metals that may be present in said particles, mention may bemade, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt,Va, Rb, W, Zn, Ge, Te and Se, and mixtures or alloys thereof. Ag, Au,Cu, Al, Zn, Ni, Mo and Cr and mixtures or alloys thereof (for examplebronzes and brasses) are preferred metals.

The term “metal derivatives” is intended to denote compounds derivedfrom metals, especially oxides, fluorides, chlorides and sulfides.

Among the metal derivatives that may be present in said particles,mention may be made especially of metal oxides, for instance titaniumoxide, especially TiO₂, iron oxide, especially Fe₂O₃, tin oxide,chromium oxide, barium sulfate and the following compounds: MgF₂, CrF₃,ZnS, ZnSe, SiO₂, Al₂O₃, MgO, Y₂O₃, SeO₃, SiO, HfO₂, ZrO₂, CeO₂, Nb₂O₅,Ta₂O₅, MoS₂, and mixtures or alloys thereof.

Illustrations of these particles that may be mentioned include aluminumparticles, such as those sold under the names Starbrite 1200 EAC® by thecompany Siberline and Metalure® by the company Eckart.

Mention may also be made of metal powders of copper or of alloy mixturessuch as the references 2844 sold by the company Radium Bronze, metallicpigments, for instance aluminum or bronze, such as those sold under thenames Rotosafe 700 from the company Eckart, silica-coated aluminumparticles sold under the name Visionaire Bright Silver from the companyEckart, and metal alloy particles, for instance the silica-coated bronze(alloy of copper and zinc) powders sold under the name Visionaire BrightNatural Gold from the company Eckart.

As illustrations of particles of this second type, mention may be mademore particularly of:

Glass particles coated with a metallic layer, especially those describedin documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460and JP-A-05017710.

As illustrations of these particles comprising a glass substrate,mention may be made of those coated, respectively, with silver, gold ortitanium, in the form of platelets, sold by the company Nippon SheetGlass under the name Microglass Metashine. Particles with asilver-coated glass substrate, in the form of platelets, are sold underthe name Microglass Metashine REFSX 2025 PS by the company Toyal.Particles with a glass substrate coated with nickel/chromium/molybdenumalloy are sold under the name Crystal Star GF 550 and GF 2525 by thissame company. Those coated either with brown iron oxide or with titaniumoxide, tin oxide or a mixture thereof, for instance those sold under thename Reflecks by the company Engelhard or those sold under the nameMetashine MC 2080GP by the company Nippon Sheet Glass.

These metal-coated glass particles may be coated with silica, forinstance those sold under the name Metashine series PSS1 or GPS1 by thecompany Nippon Sheet Glass.

Particles comprising a spherical glass substrate optionally coated witha metal, especially those sold under the name Prizmalite Microsphere bythe company Prizmalite Industries.

Pigments of the Metashine 1080R range sold by the company Nippon SheetGlass Co. Ltd are also suitable for the invention. These pigments, moreparticularly described in patent application JP 2001-11340, are C-Glassglass flakes comprising 65% to 72% SiO₂, coated with a layer of titaniumoxide of rutile type (TiO₂). These glass flakes have a mean thickness of1 micron and a mean size of 80 microns, i.e. a mean size/mean thicknessratio of 80. They have blue, green or yellow tints or a silver shadedepending on the thickness of the TiO₂ layer.

Particles comprising a silver-coated borosilicate substrate, are alsoknown as “white nacres”.

Particles comprising a metal substrate such as aluminum, copper orbronze, in the form of platelets, are sold under the trade nameStarbrite by the company Silberline and under the name Visionaire by thecompany Eckart.

Particles comprising a synthetic mica substrate coated with titaniumdioxide, and for example particles with a size of between 80 and 100 μm,comprising a synthetic mica (fluorophlogopite) substrate coated withtitanium dioxide representing 12% of the total weight of the particle,sold under the name Prominence by the company Nihon Koken.

The particles with a metallic tint may also be chosen from particlesformed from a stack of at least two layers with different refractiveindices. These layers may be of polymeric or metallic nature and mayespecially include at least one polymer layer.

Thus, the particles with a metallic effect may be particles derived froma multilayer polymer film.

The choice of materials intended to constitute the various layers of themultilayer structure is obviously made so as to give the particles thusformed the desired metallic effect.

Such particles are especially described in WO 99/36477, U.S. Pat. No.6,299,979 and U.S. Pat. No. 6,387,498 and more particularly identifiedbelow in the goniochromatic section.

Advantageously, the particles with a metallic tint in accordance withthe invention are particles with a spherical or non-spherical glasssubstrate, and also particles with a metallic substrate.

According to a specific embodiment, a composition according to theinvention contains at least reflective particles in particular selectedthe nacres, particles with a metallic tint, and bismuth oxichloride andtheir mixtures.

As illustrations of particles of this second type, mention may be mademore particularly of:

-   -   Particles comprising a synthetic mica substrate coated with        titanium dioxide coated or particles comprising a spherical        glass substrate optionally coated with either with brown iron        oxide or with titanium oxide, tin oxide or a mixture thereof,        for instance those sold under the name Reflecks by the company        Engelhard or those sold under the name Metashine MC 2080GP by        the company Nippon Sheet Glass. Such particles are detailed in        JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and        JP-A-05017710.    -   Particles with metallic effect comprising mineral substrate        coated with a metal. It may be a particles having a        silver-coated borosilicate substrate, are also known as “white        nacres.    -   Particles comprising a spherical glass substrate coated with        silver, especially those sold under the name MICROGLASS        METASHINE REFSX 2025 PS by TOYAL. Particles comprising a        spherical glass substrate coated with nickel/chrome/molybdene        alloy especially those sold under the name CRYSTAL STAR GF 550,        GF 2525 by the same company.    -   Particles having metallic effect and having on surface a        metallic compound optionally coated particles sold under the        names METASHINE® LE 2040 PS, METASHINE® 5 MC5090 PS or        METASHINE® MC280GP (2523) by the company NIPPON SHEET GLASS,        SPHERICAL SILVER POWDER® DC 100, SILVER FLAKE® JV 6 or GOLD        POWDER® A1570 by the company ENGELHARD, STARLIGHT REFLECTIONS        FXM® by the company ENERGY STRATEGY ASSOCIATES INC, BRIGHT        SILVER® 1 E 0.008×0.008 by the company MEADOWBROOK INVENTIONS,        ULTRAMIN® (ALUMINUM POUDRE FINE LIVING), and COSMETIC METALLIC        POWDER VISIONNAIRE BRIGHT SILVER SEA®, COSMETIC METALLIC POWDER        VISIONAIRE NATURAL GOLD® (60314) or COSMETIC METALLIC POWDER        VISIONAIRE HONEY® 560316° by the company ECKART.

More preferably, these reflective particles are chosen in the groupconsisting of’ bismuth oxichloride particles, mica particles coated withtitanium oxide, and mixtures thereof.

According to a specific embodiment, a composition of the inventioncontains at least bismuth oxichloride (CI 77163).

Advantageously, a composition of the invention may also contains atleast nacres comprising a silver-coated borosilicate substrate, are alsoknown as “white nacres”. Such particles are sold by the firm MERCK underthe tradename Xirona Silver.

The composition may comprise reflective particles pre-dispersed in oneoil selected from mineral, vegetable oils and ester oils.

According to a preferred embodiment, these reflective particles arepresent in the compositions of the invention under a pre-dispersed formin at least one oil selected in the group consisting of

-   -   Mineral oils    -   Vegetable oils like sweet almond oil, wheat germ oil, jojoba        oil, apricot oil, soybean oil, canola oil, castor oil;    -   Esters such as octyl dodecanol, octyldodecyl neopentanoate,        caprylic/capric triglycerides, pentaerythrityl tetraisostearate,        isodecyl neopentanoate, diisopropyl sebacate, C₁₂-C₁₅ alkyl        benzoate, ethylhexyl ethylhexanoate, ethylhexyl hydroxystearate,    -   and mixture thereof.

More preferably, the oil is chosen in the group consisting of ethyl (2)hexyl hydroxystearate, or castor oil, and preferably ethyl (2) hexylhydroxystearate.

Thus, according to a specific and preferred embodiment, a composition ofthe invention comprises, in a physiologically acceptable medium,

-   -   (i) at least microcapsules of the invention and    -   (ii) At least reflective particles under a pre-dispersed form in        at least one oil selected in the group consisting of ethyl (2)        hexyl hydroxystearate or castor oil and preferably ethyl (2)        hexyl hydroxystearate.

Advantageously, the reflective particles are chosen among bismuthoxichloride particles and mica particles covered with titanium oxide,said particles being pre-dispersed ethyl (2) hexylhydroxystearate.

According to a specific embodiment, the composition of the inventioncomprises a pre-dispersion comprising from 68% to 72% by weight ofbismuth oxichloride in 28% to 32% by weight of ethyl (2)hexylhydroxystearate, with respect to the total weight of thepre-dispersion i.e. a weight ratio bismuth oxichloride/oil(s) greater orequal to 2, and preferably ranging from 2 to 2.6.

Such a dispersion is sold by the firm MERCK under the tradename XironaSilver.Biron® Liquid Silver.

Additional Moisturizers

For a particular care application, a composition according to theinvention may comprise at least one additional moisturizer (also knownas a humectant).

The moisturizer(s) may be present in the composition in a contentranging from 0.1% to 15% by weight, especially from 0.5% to 10% byweight or even from 1% to 6% by weight, relative to the total weight ofthe said composition.

Polyhydric alcohols, preferably of C₂-C₈ and more preferably C₃-C₆,preferably such as glycerol, propylene glycol, 1,3-butylene glycol,pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycoland diglycerol, and mixtures thereof, glycerol and derivatives thereofare known as moisturizers or humectants.

The composition according to the invention may also comprise anadditional moisturizers or humectants.

These additional moisturizers or humectants that may especially bementioned include sorbitol, glycol ethers (especially containing from 3to 16 carbon atoms) such as mono-, di- or tripropylene glycol(C₁-C₄)alkyl ethers, mono-, di- or triethylene glycol (C₁-C₄)alkylethers, urea and derivatives thereof, especially Hydrovance(2-hydroxyethylurea) sold by National Starch, lactic acids, hyaluronicacid, AHAs, BHAs, sodium pidolate, xylitol, serine, sodium lactate,ectoin and derivatives thereof, chitosan and derivatives thereof,collagen, plankton, an extract of Imperata cylindra sold under the nameMoist 24 by the company Sederma, acrylic acid homopolymers, for instanceLipidure-HM® from NOF Corporation, beta-glucan and in particular sodiumcarboxymethyl beta-glucan from Mibelle-AG-Biochemistry; a mixture ofpassionflower oil, apricot oil, corn oil and rice bran oil sold byNestle under the name NutraLipids®; a C-glycoside derivative such asthose described in patent application WO 02/051 828 and in particularC-β-D-xylopyranoside-2-hydroxypropane in the form of a solutioncontaining 30% by weight of active material in a water/propylene glycolmixture (60/40% by weight) such as the product manufactured by Chimexunder the trade name Mexoryl SBB®; an oil of musk rose sold by Nestle;spheres of collagen and of chondroitin sulfate of marine origin(Atelocollagen) sold by the company Engelhard Lyon under the name MarineFilling Spheres; hyaluronic acid spheres such as those sold by thecompany Engelhard Lyon; arginine, argan oil, and mixtures thereof.

Preferably, use will be made of a moisturizer chosen from glycerol, ureaand derivatives thereof, especially Hydrovance® sold by National Starch,a C-glycoside derivative such as those described in patent applicationWO 02/051 828 and in particular C-β-D-xylopyranoside-2-hydroxypropane inthe form of a solution containing 30% by weight of active material in awater/propylene glycol mixture (60/40% by weight) such as the productmanufactured by Chimex under the trade name Mexoryl SBB®; argan oil, andmixtures thereof.

More preferably, glycerol will be used.

Sunscreen/Sunblock Agents

Sunscreens are important skin-care products used to prevent photoagingand skin cancer. There are two groups of sunscreens: UVA sunscreens,which block UV radiation in the wavelength range of about 320 to 400 nm,and UVB sunscreens, which block radiation in the range of 290 to 320 nm.

The compositions in accordance with the invention comprise organicand/or inorganic UV sunscreen ingredients active in the UV-A and/or UV-Bregion which are hydrophilic and/or lipophilic.

In particular, the UV sunscreen ingredients according to the inventionmight have a solubility parameter ranging from 8.0 to 9.5. Said UVsunscreen ingredients have a good plasticizer function.

Advantageously, the UV sunscreen agent according to the invention mighthave a molecular weight ranging from 150 to 500 g/mol and containhydrophobic sites and benzene nucleus or electron resonance groupbinding with polar sites.

The hydrophilic and/or lipophilic organic UV sunscreen ingredients areselected in particular from benzylidene camphor derivatives,dibenzoylmethane derivatives; cinnamic derivatives; salicylicderivatives; benzophenone derivatives; β,β-diphenylacrylate derivatives;p-aminobenzoic acid (PABA) derivatives; and their mixtures.

Mention may be made, as examples of organic UV sunscreen ingredients, ofthose denoted below under their INCI names:

Para-Aminobenzoic Acid Derivatives:

-   -   PABA,    -   Ethyl PABA,    -   Ethyl Dihydroxypropyl PABA,    -   Ethylhexyl Dimethyl PABA, marketed in particular under the        trademark “Escalol 507” by ISP,    -   Glyceryl PABA,

Dibenzoylmethane Derivatives:

-   -   Butyl Methoxydibenzoylmethane, marketed in particular under the        trademark “Parsol 1789” by Hoffmann-LaRoche,    -   Isopropyl Dibenzoylmethane,

Salicylic Derivatives:

-   -   Homosalate, marketed under the trademark “Eusolex HMS” by        Rona/EM Industries,    -   Ethylhexyl Salicylate, marketed under the trademark “Neo        Heliopan OS” by Haarmann and Reimer,    -   Dipropyleneglycol Salicylate, marketed under the trademark        “Dipsal” by Scher,    -   TEA Salicylate, marketed under the trademark “Neo Heliopan TS”        by Haarmann and Reimer,

Cinnamic Derivatives:

-   -   Ethylhexyl Methoxycinnamate, marketed in particular under the        trademark “Parsol MCX” by Hoffmann-LaRoche,    -   Isopropyl Methoxycinnamate,    -   Isoamyl Methoxycinnamate, marketed under the trademark “Neo        Heliopan E 1000” by Haarmann and Reimer,    -   Cinoxate,    -   DEA Methoxycinnamate,    -   Diisopropyl Methylcinnamate,    -   Glyceryl Ethylhexanoate Dimethoxycinnamate,

β,β-Diphenylacrylate Derivatives:

-   -   Octocrylene, marketed in particular under the trademark “Uvinul        N539” by BASF,    -   Etocrylene, marketed in particular under the trademark “Uvinul        N35” by BASF,

Benzophenone Derivatives:

-   -   Benzophenone-1, marketed under the trademark “Uvinul 400” by        BASF,    -   Benzophenone-2, marketed under the trademark “Uvinul D50” by        BASF,    -   Benzophenone-3 or Oxybenzone, marketed under the trademark        “Uvinul M40” by BASF,    -   Benzophenone-4, marketed under the trademark “Uvinul MS40” by        BASF,    -   Benzophenone-5,    -   Benzophenone-6, marketed under the trademark “Helisorb 11” by        Norquay,

Benzylidene Camphor Derivatives:

-   -   Terephthalylidene dicamphor sulfonic acid,    -   4-Methylbenzylidene camphor

and their mixtures.

The organic UV filter is selected from an aminobenzoic acid derivative,a dibenzoylmethane derivative, a salicylic acid derivative, a cinnamicderivative, a β,β diphenylacrylate derivative, a benzophenonederivative, benzylidene camphor derivative, and mixtures thereof.

The preferred UV sunscreen ingredients are selected in the groupconsisting of cinnamic derivatives, β,β diphenylacrylates derivatives,salicylic derivatives, and their mixtures.

The preferred UV sunscreen ingredients are especially selected in thegroup consisting of ethylhexyl methoxycinnamate, octocrylene andethylhexyl salicylate, and their mixtures.

Mention may be made especially of ethylhexyl methoxycinnamate sold underthe tradename UVINUL MC 80® by the company BASF, of ethylhexylsalicylate sold under the tradename NEO HELIOPAN OS® by the companySYMRISE and of octocrylene sold under the tradename NEO HELIOPAN 303® bythe company SYMRISE.

The composition in accordance with the invention may comprise from 0.1°A to 30% by weight, for example from 0.5 to 20% by weight, for examplefrom 1 to 15% by weight, and for example at least 1% by weight, of UVsunscreen ingredient relative to the total weight of the composition.

According to one exemplary embodiment, the composition may comprise themicrocapsules and at least one UV sunscreen ingredient in a weight ratio[mineral filler/UV sunscreen ingredient] ranging from 0.20 to 10, forexample from 1 to 9.5, preferably from 3 to 9.

Advantageously, the composition of the invention comprises at least oneUV filter and eventually an active agent.

Active Agents

For application in particular for caring for or making up skin, thecomposition according to the invention may comprise at least one activeagent chosen from:

According to one advantageous embodiment, the combination according tothe invention may be combined with one or more supplementary cosmeticactive agents.

These active agents may be chosen from antiwrinkle agents vitamins, inparticular B3, B8, B12 and B9, moisturizers, desquamating agents,anti-ageing active agents, depigmenting agents, antioxidants, etc.

These active agents may be present in the composition in a contentranging from 0.001% to 20% by weight, preferably from 0.01% to 10% byweight, and more preferably from 0.01% to 5% by weight, relative to thetotal weight of the composition.

Antiwrinkle agents: mention may be made to ascorbic acid and derivativesthereof, such as magnesium ascorbyl phosphate and ascorbyl glucoside;tocopherol and derivatives thereof, such as tocopheryl acetate;nicotinic acid and precursors thereof, such as nicotinamide; ubiquinone;glutathione and precursors thereof, such asL-2-oxothiazolidine-4-carboxylic acid; C-glycoside compounds andderivatives thereof, as described in particular hereinafter: extracts ofplants, and in particular extracts of sea fennel and of olive leaf; andalso plant proteins and hydrolysates thereof, such as rice or soybeanprotein hydrolysates; algal extracts and in particular of laminaria;bacterial extracts; sapogenins, such as diosgenin and extracts ofDioscorea plants, in particular of wild yam, containing them; α-hydroxyacids; β-hydroxy acids, such as salicylic acid and 5-n-octanoylsalicylicacid; oligopeptides and pseudodipeptides and acyl derivatives thereof,in particular{2-[acetyl-(3-trifluoromethylphenyl)amino]-3-methyl-butyrylamino}aceticacid and the lipopeptides sold by the company Sederma under the tradenames Matrixyl 500 and Matrixyl 3000; lycopene; manganese salts andmagnesium salts, in particular manganese and magnesium gluconates; andmixtures thereof;

-   -   Desquamating agents: mention will be made of beta-hydroxy acids,        in particular salicylic acids and derivatives thereof other than        5-n-octanoylsalicylic acid; urea; glycolic acid, citric acid,        lactic acid, tartaric acid, malic acid or mandelic acid;        4-(2-hydroxyethyl)piperazine-1-propanesulphonic acid (HEPES);        extract of Saphora japonica; honey; N-acetylglucosamine; sodium        methylglycine diacetate, alpha-hydroxy acids (ANAs),        beta-hydroxy acids (BHAs), and mixtures thereof;    -   Depigmenting agents: mention may be made of ceramides, vitamin C        and derivatives thereof, in particular vitamin CG, CP and 3-0        ethyl vitamin C, alpha- and beta-arbutin, ferulic acid, kojic        acid, resorcinol and derivatives thereof, calcium D-pantetheine        sulphonate, lipoic acid, ellagic acid, vitamin B3, phenylethyl        resorcinol, for instance Symwhite 377® from the company Symrise,        a kiwi fruit (Actinidia chinensis) juice sold by Gattefosse, an        extract of Paeonia suffructicosa root, such as the product sold        by the company Ichimaru Pharcos under the name Botanpi Liquid        B®, an extract of brown sugar (Saccharum officinarum), such as        the extract of molasses sold by the company Taiyo Kagaku under        the name Molasses Liquid, a mixture of undecylenic acid and        undecylenoyl phenyl alanine, such as Sepiwhite MSH® from Seppic;    -   Antioxidants: mention may more particularly be made of        tocopherol and esters thereof, in particular tocopheryl acetate;        EDTA, ascorbic acid and derivatives thereof, in particular        magnesium ascorbyl phosphate and ascorbyl glucoside; chelating        agents, such as BHT, BHA,        N,N′-bis(3,4,5-trimethoxybenzyl)ethylenediamine and its salts,        and mixtures thereof.

When the active principle ascorbyl glucoside is present in the cosmeticcomposition according to the present invention, it is present in anamount lower than 0.05% by weight, and more preferably of 0.01% byweight relative to the total weight of the composition.

Galenic Formulation

A gel composition according to the invention may be in the form ofmakeup compositions and/or care compositions for keratin materials, inparticular for skin or lips.

Particularly, a composition according to the invention may be a BBproduct or a foundation especially to be applied on the face or neck, aproduct for masking dark circles, a concealer product, a tinted cream, acolored composition for care or for making up the skin, especially forthe face or body or an after-sun composition.

In a preferred embodiment, a composition according to the presentinvention is a non-rinsing composition: the composition is not intendedto be rinsed after application on the skin.

In another preferred embodiment, the composition according to thepresent invention is not contained in a dispenser comprising a pump.This is advantageous since it avoids the risk for the microcapsules tobe broken. Indeed, when using such a dispenser, said microcapsules couldbe crushed before their application on the keratin materials.

A gel composition according to the invention may comprise at least onesurfactant (emulsifier), chosen especially from amphoteric, anionic,cationic and nonionic surfactants, used alone or as a mixture.

The surfactants are generally present in the composition in a proportionthat may range, for example, from 0.3% to 20% by weight, in particularfrom 0.5% to 15% by weight and more particularly from 1% to 10% byweight of surfactants relative to the total weight of the composition.These compositions are prepared according to the usual methods.

For example, when the emulsifier potassium cetyl phosphate is present inthe cosmetic composition according to the present invention, it is in aproportion that may range, for example, from 0.2% to 3% by weight, moreparticularly from 0.5% to 1.5% by weight and more preferably from 0.8%to 1.2% by weight, and even more preferably 1′)/0 by weight relative tothe total weight of the composition.

Throughout the description, including the claims, the term “comprisinga” should be understood as being synonymous with “comprising at leastone”, unless otherwise mentioned.

The terms “between . . . and . . . ” and “ranging from . . . to . . . ”should be understood as being inclusive of the limits, unless otherwisespecified.

The invention is illustrated in greater detail by the examples accordingto the invention described below. Unless otherwise mentioned, theamounts indicated are expressed as mass percentages of active material.

EXAMPLES

I Microcapsules

Different examples of preparation of microcapsules according to theinvention are here below described for illustrating the invention.

Example 1: Preparation of a Microcapsule Having Inner Brown ColorCoating and Outer White Color Coating

Mannitol (spray dried mannitol: Pearitol 100SD) is used as core.

To a mixed solution of 1600.0 g of methylene chloride and 1600.0 g ofethanol, 120.0 g of ceramide (Ceramide PC 104) and 120.0 g ofhydrogenated lecithin (Lipoid S 100-3) are added and completelydissolved at 40° C. To the resulting mixture, 1260.0 g of iron oxideyellow, 252.0 g of iron oxide red and 45.36 g of iron oxide black areadded and well dispersed with a homogenizer to prepare an inner colorcoating solution.

347.70 g of Mannitol is introduced into a fluidized bed coating system(Glatt GPOG 1, bottom spray) as a seed and subjected to a coating at 500ml/h of feeding rate of the inner color coating solution to obtainparticles having a mannitol core coated with an inner color layer.

Thereafter, to a mixed solution of 720.0 g of methylene chloride and720.0 g of ethanol, 36.0 g of ceramide and 36.0 g of hydrogenatedlecithin are added and dissolved at 40° C. To the resulting mixture,600.0 g of titanium dioxide particles are added and well dispersed witha homogenizer to prepare a titanium dioxide particle coating solution.

A coating with the resulting titanium dioxide particle coating solutionis realized by a fluidized bed process to obtain particles having aninner color layer coated with a titanium dioxide particle layer.

Then, 300.0 g of shellac is dissolved in 3000 g of ethanol to prepare anouter layer coating solution, which is coated onto the above titaniumdioxide particle layer to obtain a color-changing microcapsule having atitanium dioxide particle layer coated with an outer layer.

Example 2: Preparation of a Microcapsule Having Inner Yellow ColorCoating and Outer White Color Coating

A microcapsule is prepared in the same manner as in Example 1 except forusing 1557.36 g of iron oxide yellow instead of the mixed colorantsconsisting of iron oxide yellow, iron oxide red and iron oxide black asthe inner color in the preparation of the inner color coating solution.

Example 3: Preparation of a Microcapsule Having Inner Red Color Coatingand Outer White Color Coating

A microcapsule is prepared in the same manner as in Example 1 except forusing 1557.36 g of iron oxide red instead of the mixed colorantsconsisting of iron oxide yellow, iron oxide red and iron oxide black asthe inner color in the preparation of the inner color coating solution.

Example 4: Preparation of a Microcapsule Having Inner Black ColorCoating and Outer White Color Coating

A microcapsule is prepared in the same manner as in Example 1 except forusing 1557.36 g of iron oxide black instead of the mixed colorantsconsisting of iron oxide yellow, iron oxide red and iron oxide black asthe inner color in the preparation of the inner color coating solution.

Example 5: Preparation of a Microcapsule Having Inner Black ColorCoating and Outer Green Color Coating

The same procedure as in Example 4 is repeated to the step for forming atitanium dioxide particles layer.

Thereafter, to a mixed solution of 400.0 g of methylene chloride and400.0 g of ethanol, 20.0 g of ceramide and 20.0 g of hydrogenatedlecithin are added and dissolved at 40° C. To the resulting reactionmixture, 40.0 g of chromium hydroxide green (C177289) is added and welldispersed with a homogenizer to prepare a green color coating solution.

A coating with the resulting green color coating solution is realized bya fluidized bed process at 500 ml/h of feeding rate of the coatingsolution to obtain particles having a titanium dioxide particle layercoated with a green color layer.

Then, 200.0 g of polymethacrylate (Eudragit RSPO) is dissolved in 4000 gof ethanol to prepare an outer layer coating solution. A coating withthe resulting outer layer coating solution is realized by a fluidizedbed process at 100 ml/h of feeding rate of the coating solution toobtain a color-changing microcapsule having a green color layer coatedwith a polymeric outer layer.

Example 6

By using the ingredients and contents described in the below table, acolor-changing microcapsule having a core and 2 layers as shown in FIG.2 is prepared by a fluidized bed process:

(1) Mixed Pigment (Inner color): Yellow:Red:Black=55.18:34.48:10.34

(2) Ingredients: Core seed-Inner color layer-TiO₂ particle layer

Core Mannitol 16.45%  1^(st) layer Mixed Pigment 50.0%  Lecithin 0.4%Corn Starch binder 2.0% 2^(nd) layer Titanium dioxide qsp. 100% Lecithin0.2% Corn Starch binder 0.8%

Percentages indicate weight percent relative to the total microcapsuleweight.

Example 7

By using the ingredients and contents described in the below table, acolor-changing microcapsule having a core and 3 layers as shown in FIG.3 is prepared by a fluidized bed process:

(1) Mixed Pigment (Inner color): Yellow:Red:Black=60.4:23.8:11.4:4.4

(2) Ingredients: Core seed-Inner color layer-TiO₂ particle layer-outercolor layer

Core Mannitol 6.5% 1^(st) layer Mixed Pigment 17.8%  Sunpuro Yellow2.00%  Lecithin 5.0% Eudragit RSPO 4.0% 2^(nd) layer Titanium dioxideqsp. 100% Lecithin 5.0% Eudragit RSPO 4.0% 3^(rd) layer D&C Red30 0.8%Cornstarch binder 0.4%

Percentages indicate weight percent relative to the total microcapsuleweight.

Example 8

By using the ingredients and contents described in the below table, acolor-changing microcapsule having a core and 2 layers as shown in FIG.4 is prepared by a fluidized bed process:

(1) Mixed Pigment (Inner color): Yellow:Red:Black=60.1:28.8:11.1

(2) Ingredients: Core seed-inner color layer-TiO₂ particle layer

Core Mannitol 17.8%  1^(st) layer Mixed Pigment 19.8%  Lecithin 0.2%Corn Starch binder 0.8% 2^(nd) layer Titanium dioxide qsp. 100% Mannitol5.0% Corn Starch 5.0% Lecithin 0.3% Corn Starch binder 1.2%

Percentages indicate weight percent relative to the total microcapsuleweight.

Example 9

By using the ingredients and contents described in the below table, acolor-changing microcapsule having a core and 2 layers as shown in FIG.5 is prepared by a fluidized bed process:

(1) Ingredients: Core seed-inner color layer-TiO₂ particle layer

Core Mannitol 13.7% 1^(st) layer Sunpuro Yellow 17.36%  Sunpuro Red3.67% Sunpuro Black 0.61% Lecithin 0.20% Corn Starch Binder  1.0% 2^(nd)layer Titanium dioxide qsp. 100% Lecithin  0.3% Corn Starch Binder  1.5%

Percentages indicate weight percent relative to the total microcapsuleweight.

Example 10

By using the ingredients and contents described in the below table, acolor-changing microcapsule having a core and 3 layers as shown in FIG.6 is prepared by a fluidized bed process:

(1) Mixed Pigment (Inner color): Yellow:Red:Black=55.18:34.48:10.34

(2) Ingredients: Core seed-Inner color layer-TiO₂ particle layer-Outercolor layer

Core Mannitol 16.81%  1^(st) layer Mixed Pigment 49.15%  Lecithin 0.29% Corn Starch Binder 1.97%  2^(nd) layer Titanium dioxide qsp 100%%Lecithin 0.1% Corn Starch Binder 0.49%  3^(rd) layer Sunpuro Yellow 1.0%Sunpuro Red 0.2% Corn Starch Binder 0.5%

Percentages indicate weight percent relative to the total microcapsuleweight.

Example 11

By using the ingredients and contents described in the below table, acolor-changing microcapsule having a core and 3 layers as shown in FIG.7 is prepared by a fluidized bed process:

(1) Mixed Pigment (Inner color): White:Yellow:Red=92:6:2

(2) Ingredients: Core seed-Inner color layer-TiO₂ particle layer-Outercolor layer

Core  4.0% Cellulose 1.12% Mannitol  1.0% Zea Mays (corn) starch 1.84%Hydrogenated Lecithin 0.04% 1^(st) layer Mixed Pigment 55.0% TitaniumDioxide 50.6% Iron oxide Yellow  3.3% Iron oxide Red  1.1% Lecithin0.50% Hydrogenated Lecithin 0.50% Mannitol  3.5% Mannitol  3.5% CornStarch Binder  2.0% Zea Mays (corn) starch  2.0% 2^(nd) layer Titaniumdioxide qsp 100%. Titanium dioxide qsp 100%. Corn Starch 3.62% Zea Mays(corn) starch 3.62% Cellulose  9.0% Cellulose  9.0% Mannitol 13.0%Mannitol 13.0% Lecithin 0.25% Hydrogenated Lecithin 0.25% Corn StarchBinder  1.8% Zea Mays (corn) starch  1.8% 3^(rd) Satin White  1.8%Synthetic 1.035%  Layer Fluorphlogopite Tin oxide 0.009%  TitaniumDioxide 0.756%  D&C Red30 0.03% Red30 Al. Lake 0.03% Corn Starch Binder 0.5% Zea Mays (corn) starch  0.5%

Percentages indicate weight percent relative to the total microcapsuleweight.

Example 12

By using the ingredients and contents described in the below table, acolor-changing microcapsule having a core and 3 layers as shown in FIG.8 is prepared by a fluidized bed process:

(1) Mixed Pigment (Inner color): White:Yellow:Red:Black=89:2:8:1

(2) Ingredients: Core seed-Inner color layer-TiO₂ particle layer-Outercolor layer

Core 34.4%  1^(st) layer Mixed Pigment 50.0%  Lecithin 0.50%  Mannitol4.0% Corn Starch Binder 2.0% 2^(nd) layer Titanium dioxide qsp 100%Lecithin 0.1% Corn Starch Binder 0.4% 3^(rd) Layer C. Monarch gold 3.0%Corn Starch Binder 0.6%

Percentages indicate weight percent relative to the total microcapsuleweight.

(3) Ingredient of each layer (in details):

Core 34.4%  Zea Mays (corn) Starch 14.3%  Mannitol 10.5%  Cellulose 9.6%1^(st) layer Mixed Pigment 50.0%  Titanium Dioxide 44.5%  Iron oxideYellow 4.0% Iron oxide Red 1.0% Iron oxide Black 0.5% Lecithin 0.50% Hydrogenated Lecithin 0.50%  Mannitol 4.0% Mannitol 4.0% Corn StarchBinder 2.0% Zea Mays (corn) Starch 2.0% 2^(nd) layer Titanium dioxideqsp. 100% Titanium dioxide qsp. 100% Lecithin 0.1% Hydrogenated Lecithin0.1% Corn Starch Binder 0.4% Zea Mays (corn) Starch 0.4% 3^(rd) Layer C.Monarch gold 3.0% Mica 1.575%  Titanium Dioxide 1.29%  Iron oxide Red0.12%  Tin Oxide 0.015%  Corn Starch Binder 0.6% Zea Mays (corn) Starch0.6%Percentages indicate weight percent relative to the total microcapsuleweight.

Example 13

By using the ingredients and contents described in the below table, acolor-changing microcapsule having a core and 2 layers as shown in FIG.9 is prepared by a fluidized bed process:

(1) Ingredients: Core seed-White TiO₂ particle layer-Outer color layer

Core Mannitol 27.85%  1^(st) layer Titanium dioxide qsp. 100% Lecithin0.5% Corn Starch Binder 1.5% 2^(nd) layer D&C Red30 0.145%  Satin White4.55%  Corn Starch Binder 0.3%Percentages indicate weight percent relative to the total microcapsuleweight.

(2) Ingredient of each layer (in details):

Core Mannitol 27.85% Mannitol 27.85% 1^(st) layer Titanium dioxide qsp.Titanium dioxide qsp.   100% Lecithin  0.5% Lecithin  0.5% Corn StarchBinder  1.5% Corn Starch Binder  1.5% 2^(nd) layer D&C Red30 0.145% D&CRed30 0.145% Satin White  4.55% Synthetic  2.66% Fluorphlogopite Tinoxide 0.023% Titanium Dioxide 1.867% Corn Starch Binder  0.3% CornStarch Binder  0.3%

Percentages indicate weight percent relative to the total microcapsuleweight.

Example 14

By using the ingredients and contents described in the below table, acolor-changing microcapsule having a core and 3 layers as shown in FIG.10 is prepared by a fluidized bed process:

(1) Mixed Pigment: White:Yellow:Red:Black=84.3:5.0:8.7:2

(2) Ingredients: Core seed-Inner color layer-TiO₂ particle layer-Outmostshell

Core 4.0% Cellulose 1.0% Mannitol 1.0% Zea Mays (corn) Starch 2.0%1^(st) Mixed Pigment 50.0%  Titanium dioxide 42.15%  layer Iron oxideYellow 2.5% Iron oxide Red 4.35%  Iron oxide Black 1.0% Lecithin 0.50% Hydrogenated Lecithin 0.50%  Mannitol 3.5% Mannitol 3.5% Corn Starch2.0% Zea Mays (corn) Starch 2.0% Binder 2^(nd) Titanium dioxide qsp.Titanium dioxide qsp. layer 100% 100% Corn Starch 2.0% Zea Mays (corn)Starch 2.0% Cellulose 5.0% Cellulose 5.0% Mannitol 6.5% Mannitol 6.5%Lecithin 0.25%  Hydrogenated Lecithin 0.25%  Corn Starch 1.0% Zea Mays(corn) Starch 1.0% Binder 3^(rd) Iron oxide Red 0.05%  Iron oxide Red0.05%  Layer Iron oxide Yellow 0.01%  Iron oxide Yellow 0.01%  Cellulose5.0% Cellulose 5.0% Mannitol 6.5% Mannitol 6.5% Corn Starch 7.44%  ZeaMays (corn) Starch 7.44%  Lecithin 0.25%  Hydrogenated Lecithin 0.25% Corn Starch 1.0% Zea Mays (corn) Starch 1.0% Binder

Percentages indicate weight percent relative to the total microcapsuleweight.

II Compositions

In all examples, <<alcohol>> means <<ethanol>>.

When not specified, the protocol used to prepare the compositions is aconventional protocol.

Example 1: Transparent Gel with Brown Microcapsules for Make-Up Result

Phase INCI name % weight A1 WATER qsp 100 ACRYLATES/C10-30 ALKYLACRYLATE 0.70 CROSSPOLYMER (CARBOPOL ULTREZ 20 POLYMER ® from LUBRIZOL)A2 GLYCERIN 4.00 DISODIUM EDTA 0.15 BUTYLENE GLYCOL 6.00 CAPRYLYL GLYCOL0.25 B WATER 31.00 BIS-PEG-18 METHYL ETHER DIMETHYL 2.00 SILANE (DOWCORNING 2501 COSMETIC WAX ® from Dow Corning) C WATER 3.00 D1BIOSACCHARIDE GUM-1 1.00 PEG/PPG/POLYBUTYLENE GLYCOL-8/5/3 0.70 GLYCERIN(WILBRIDE S-753L ® from Nof Corporation) D2 ALCOHOL 4.00 E TITANIUMDIOXIDE (and) IRON OXIDES 2 (and) MANNITOL (and) IRON OXIDES (and) ZEAMAYS (CORN) STARCH (and) IRON OXIDES (and) HYDROGENATED LECITHIN(Magic50-BW0105 ® from KPT)Protocol of Preparation:

Premix B at 70° C., mix until solution is clear

Main Mix

1. Phase A1 make the polymer well swelled in water, then, heat to 80°C.-85° C.

2. Add A2, mix until fully dissolved

3. Add phase B, fully dissolved, then cool to RT

4. Below 40° C., add in phase C.

5. Vacuum and slow mix, to reduce the gas bubbles in the bulk

6. Add phase D1, D2

7. Vacuum and slow mix, until temp to RT, and with few gas bubbles

8. Slowly add phase E (microcapsules), mix without scraper.

9. When microcapsules are fully dispersed evenly, stop mixing, check thepH and viscosity

The viscosity of the gel is around 20 UD (Mobile 3) by Rheomat RM180, at25° C. according to the protocol disclosed above.

Aspect of the Composition and Evaluation after Application

The gel presents a transparent and caring appearance and also coveringmakeup effects.

We obtain a gel with colored microcapsules in pure and clean appearance,with perfect stability under −20/20° C. (5 cycle), room temperature (25°C., 2 months), 37° C. (2 months) and 45° C. (2 months). Themicrocapsules release pigments during application on the skin withcomfortable feeling during application, and confer natural make-upresult as it was a foundation, but with a very good balance of skincareefficacy perception (watery, moisturization and transparent) as well asmakeup efficacy (proper coverage).

Example 2: Skin Care Gel

INCI name % weight WATER Qsp 100 GLYCERIN 4 DISODIUM EDTA 0.15NIACINAMIDE 4 BUTYLENE GLYCOL 7 CHLORPHENESIN 0.25 ACRYLATES/C10-30ALKYL ACRYLATE 0.7 CROSSPOLYMER (CARBOPOL ULTREZ 20 POLYMER ® fromLUBRIZOL) BIS-PEG-18 METHYL ETHER DIMETHYL 2 SILANE PEG-60 HYDROGENATEDCASTOR OIL 0.1 BIOSACCHARIDE GUM-1 1 SODIUM HYDROXIDE 0.24 ALCOHOL 5CAPRYLOYL SALICYLIC ACID 0.15 TITANIUM DIOXIDE (and) MANNITOL (and) 0.5HYDROGENATED LECITHIN (and) IRON OXIDES (and) SYNTHETIC FLUORPHLOGOPITE(and) IRON OXIDES (and) RED 30 LAKE (and) IRON OXIDES (and) TIN OXIDE(and) ZEA MAYS (CORN) STARCH (Magic 60-WP0105 ® from KPT) TITANIUMDIOXIDE (and) IRON OXIDES (and) 0.2 MANNITOL (and) IRON OXIDES (and) ZEAMAYS (CORN) STARCH (and) IRON OXIDES (and) HYDROGENATED LECITHIN(Magic50- BW0105 ® from KPT)The gel is prepared as the one disclosed in example 1.

After application on the skin, natural make-up result is obtained with agood balance of skincare efficacy perception (watery, moisturization andtransparent) as well as makeup efficacy (proper coverage).

Example 3: Gelly Skin Care Gel

INCI NAME % weight WATER Qsp 100 GLYCEROL 4 1,3-BUTYLENE GLYCOL 8VITAMINE B3 OR PP:NICOTINIC ACID AMIDE 4 ETHYLENE DIAMINE TETRACETICACID, DISODIUM 0.1 SALT, 2 H2O CARBOXYVINYLIC POLYMER SYNTHETIZED IN 0.6METHYLENE CHLORIDE POLY DIMETHYLSILOXANE (VISCOSITY: 10 CST) 1 MIXTUREOF RETICULATED POLY 0.8 DIMETHYLSILOXANE POLYALKYLENE AND POLYDIMETHYLSILOXANE (6 CST) 27/73 MIXTURE OF POLY DIHYDROXYLATED 1.2DIMETHYLSILOXANE ALPHA-OMEGA/POLY DIMETHYLSILOXANE 5 CST n-OCTANOYL-5SALICYLIC ACID 0.15 NO DENATURATED ABSOLUTE ETHYL ALCOHOL 5 TITANIUMDIOXIDE (and) IRON OXIDES (and) 0.5 MANNITOL (and) IRON OXIDES (and) ZEAMAYS (CORN) STARCH (and) IRON OXIDES (and) HYDROGENATED LECITHIN(Magic50-BW0105 ® from KPT)

This gel composition is obtained according to classical method. Afterapplication on the skin, a healthy effect is obtained with a goodbalance of skincare efficacy perception (watery, moisturization andtransparent) as well as makeup natural effect.

What is claimed is:
 1. A changing colour composition in the form of agel comprising, in a physiologically acceptable medium, a) from 0.1 to10% by weight relative to the weight of the composition of microcapsulescontaining releasable colorant(s), said microcapsules comprising: a corecomprising one organic material, at least two layered coatingssurrounding said core, at least one of the layered coatings comprisingat least one polymer, at least one colorant, b) at least 3% by weightrelative to the weight of the composition of an aqueous phase comprisingwater and at least one compound chosen from polyols, glycols and C₂-C₅monoalcohols, and mixtures thereof, and c) at least one hydrophilicgelifying agent, wherein the core comprises at least onemonosaccharide-polyol selected from the group consisting of mannitol,erythritol, xylitol, sorbitol and mixtures thereof, the core does notcontain colorant material, and the microcapsules comprise at least twolayers of different colors.
 2. The changing colour composition accordingto claim 1, wherein said microcapsules further comprise at least onehydrophilic polymer.
 3. The changing colour composition according toclaim 1, wherein the gel is transparent or translucent.
 4. The changingcolour composition according to claim 1, comprising at least onehydrophilic gelifying agent chosen from water-soluble or waterdispersible polymers wherein the water-soluble or water dispersiblepolymers are chosen from: modified or unmodified carboxyvinyl polymers;polyacrylates; polymethacrylates; polyacrylamides;2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers;crosslinked anionic copolymers of acrylamide and of ammoniumpolyacryloyldimethyltaurate (AMPS); polysaccharide biopolymers;celluloses; and mixtures thereof.
 5. The changing colour compositionaccording to claim 4, wherein the water-soluble or water dispersiblepolymers are chosen from Acrylates/C₁₀₋₃₀ Alkyl Acrylate Crosspolymer;Ammonium acryloyldimethyl Taurate/Steareth-8 Methacrylate copolymer;Acrylates copolymer; Ammonium acryloyldimethyl taurate/steareth-25Methacrylate Crosspolymer; Ammonium acryloyldimethyl taurate, andxanthan gum.
 6. The changing colour composition according to claim 1,wherein the hydrophilic gelifying agent(s) are present in an amountranging from 0.001 to 10% by weight relative to the total weight of thecomposition.
 7. The changing colour composition according to claim 1,further comprising one or more water soluble emollient(s) and/orlipid(s) with a polar moiety.
 8. The changing colour compositionaccording to claim 1, wherein the microcapsules have a size ranging from50 μm to 800 μm in diameter of the microcapsule and comprise: a core(A); ii) one first layer (B) surrounding said core comprising: at leastone colorant, and a binder selected from at least one polymer, at leastone lipid-based material, and their mixture: iii) one second layer (C)surrounding said first layer (B), comprising: titanium dioxideparticles, and a binder selected from at least one polymer, at least onelipid-based material, and their mixture.
 9. The changing colour cosmeticcomposition according to claim 1, wherein the compound in part (b) ofclaim 1 is selected from polyols or glycols, and wherein said polyols orglycols are present in an amount of 12% to 50% based on the weight ofthe aqueous phase composition.
 10. The changing colour cosmeticcomposition according to claim 1, comprising water in an amount of atleast 30% by weight relative to the total weight of the composition. 11.The changing colour cosmetic composition according to claim 1,comprising an aqueous phase in a content ranging from 30% to 99% byweight relative to the total weight of the said composition.
 12. Thechanging colour cosmetic composition according to claim 1, wherein atleast one layer of the microcapsules is obtained by fluid bed process.13. The changing colour cosmetic composition according to claim 1,wherein said composition is for caring for and/or making up keratinmaterials.
 14. A cosmetic process for caring for and/or making upkeratinic materials, comprising applying on said keratinic materials acomposition as defined according to claim 1.